diff --git a/discovery/aws/ec2.go b/discovery/aws/ec2.go
index a6a0a8257..a44912481 100644
--- a/discovery/aws/ec2.go
+++ b/discovery/aws/ec2.go
@@ -42,28 +42,29 @@ import (
 )
 
 const (
-	ec2Label                  = model.MetaLabelPrefix + "ec2_"
-	ec2LabelAMI               = ec2Label + "ami"
-	ec2LabelAZ                = ec2Label + "availability_zone"
-	ec2LabelAZID              = ec2Label + "availability_zone_id"
-	ec2LabelArch              = ec2Label + "architecture"
-	ec2LabelIPv6Addresses     = ec2Label + "ipv6_addresses"
-	ec2LabelInstanceID        = ec2Label + "instance_id"
-	ec2LabelInstanceLifecycle = ec2Label + "instance_lifecycle"
-	ec2LabelInstanceState     = ec2Label + "instance_state"
-	ec2LabelInstanceType      = ec2Label + "instance_type"
-	ec2LabelOwnerID           = ec2Label + "owner_id"
-	ec2LabelPlatform          = ec2Label + "platform"
-	ec2LabelPrimarySubnetID   = ec2Label + "primary_subnet_id"
-	ec2LabelPrivateDNS        = ec2Label + "private_dns_name"
-	ec2LabelPrivateIP         = ec2Label + "private_ip"
-	ec2LabelPublicDNS         = ec2Label + "public_dns_name"
-	ec2LabelPublicIP          = ec2Label + "public_ip"
-	ec2LabelRegion            = ec2Label + "region"
-	ec2LabelSubnetID          = ec2Label + "subnet_id"
-	ec2LabelTag               = ec2Label + "tag_"
-	ec2LabelVPCID             = ec2Label + "vpc_id"
-	ec2LabelSeparator         = ","
+	ec2Label                     = model.MetaLabelPrefix + "ec2_"
+	ec2LabelAMI                  = ec2Label + "ami"
+	ec2LabelAZ                   = ec2Label + "availability_zone"
+	ec2LabelAZID                 = ec2Label + "availability_zone_id"
+	ec2LabelArch                 = ec2Label + "architecture"
+	ec2LabelIPv6Addresses        = ec2Label + "ipv6_addresses"
+	ec2LabelInstanceID           = ec2Label + "instance_id"
+	ec2LabelInstanceLifecycle    = ec2Label + "instance_lifecycle"
+	ec2LabelInstanceState        = ec2Label + "instance_state"
+	ec2LabelInstanceType         = ec2Label + "instance_type"
+	ec2LabelOwnerID              = ec2Label + "owner_id"
+	ec2LabelPlatform             = ec2Label + "platform"
+	ec2LabelPrimaryIPv6Addresses = ec2Label + "primary_ipv6_addresses"
+	ec2LabelPrimarySubnetID      = ec2Label + "primary_subnet_id"
+	ec2LabelPrivateDNS           = ec2Label + "private_dns_name"
+	ec2LabelPrivateIP            = ec2Label + "private_ip"
+	ec2LabelPublicDNS            = ec2Label + "public_dns_name"
+	ec2LabelPublicIP             = ec2Label + "public_ip"
+	ec2LabelRegion               = ec2Label + "region"
+	ec2LabelSubnetID             = ec2Label + "subnet_id"
+	ec2LabelTag                  = ec2Label + "tag_"
+	ec2LabelVPCID                = ec2Label + "vpc_id"
+	ec2LabelSeparator            = ","
 )
 
 // DefaultEC2SDConfig is the default EC2 SD configuration.
@@ -317,6 +318,7 @@ func (d *EC2Discovery) refresh(ctx context.Context) ([]*targetgroup.Group, error
 
 					var subnets []string
 					var ipv6addrs []string
+					var primaryipv6addrs []string
 					subnetsMap := make(map[string]struct{})
 					for _, eni := range inst.NetworkInterfaces {
 						if eni.SubnetId == nil {
@@ -330,6 +332,15 @@ func (d *EC2Discovery) refresh(ctx context.Context) ([]*targetgroup.Group, error
 
 						for _, ipv6addr := range eni.Ipv6Addresses {
 							ipv6addrs = append(ipv6addrs, *ipv6addr.Ipv6Address)
+							if *ipv6addr.IsPrimaryIpv6 {
+								// we might have to extend the slice with more than one element
+								// that could leave empty strings in the list which is intentional
+								// to keep the position/device index information
+								for int64(len(primaryipv6addrs)) <= *eni.Attachment.DeviceIndex {
+									primaryipv6addrs = append(primaryipv6addrs, "")
+								}
+								primaryipv6addrs[*eni.Attachment.DeviceIndex] = *ipv6addr.Ipv6Address
+							}
 						}
 					}
 					labels[ec2LabelSubnetID] = model.LabelValue(
@@ -342,6 +353,12 @@ func (d *EC2Discovery) refresh(ctx context.Context) ([]*targetgroup.Group, error
 								strings.Join(ipv6addrs, ec2LabelSeparator) +
 								ec2LabelSeparator)
 					}
+					if len(primaryipv6addrs) > 0 {
+						labels[ec2LabelPrimaryIPv6Addresses] = model.LabelValue(
+							ec2LabelSeparator +
+								strings.Join(primaryipv6addrs, ec2LabelSeparator) +
+								ec2LabelSeparator)
+					}
 				}
 
 				for _, t := range inst.Tags {
diff --git a/docs/configuration/configuration.md b/docs/configuration/configuration.md
index 5df7dae3c..164f426ad 100644
--- a/docs/configuration/configuration.md
+++ b/docs/configuration/configuration.md
@@ -1229,6 +1229,7 @@ The following meta labels are available on targets during [relabeling](#relabel_
 * `__meta_ec2_ipv6_addresses`: comma separated list of IPv6 addresses assigned to the instance's network interfaces, if present
 * `__meta_ec2_owner_id`: the ID of the AWS account that owns the EC2 instance
 * `__meta_ec2_platform`: the Operating System platform, set to 'windows' on Windows servers, absent otherwise
+* `__meta_ec2_primary_ipv6_addresses`: comma separated list of the Primary IPv6 addresses of the instance, if present. The list is ordered based on the position of each corresponding network interface in the attachment order.
 * `__meta_ec2_primary_subnet_id`: the subnet ID of the primary network interface, if available
 * `__meta_ec2_private_dns_name`: the private DNS name of the instance, if available
 * `__meta_ec2_private_ip`: the private IP address of the instance, if present