Can Amazon EC2 instances within a VPC communicate with Amazon S3?

Yes. There are multiple options for your resources within a VPC to communicate with Amazon S3. You can use VPC Endpoint for S3, which makes sure all traffic remains within Amazon's network and enables you to apply additional access policies to your Amazon S3 traffic. You can use an Internet gateway to enable Internet access from your VPC and instances in the VPC can communicate with Amazon S3. You can also make all traffic to Amazon S3 traverse the Direct Connect or VPN connection, egress from your datacenter, and then re-enter the public AWS network.