I've recently started using KOPS as a tool to provision Kubernetes clusters and from what I've seen so far, it stores it's CA key and certificates in its S3 bucket, which is fine.
But out curiosity, would it be possible to store these in Hashicorp Vault instead, as opposed to s3?
Yes. User Matt Schuchard has mentioned in the comment:
For more details look at this kops documentation. The most interesting part should be Node authentication and configuration:
Look also at this hashicorp site.