When you first open a Replay, you'll be able to toggle between the Viewer and the DevTools. The Viewer is where you're able to watch a full video replay.
You can play or scrub the video and click anywhere on the Replay to add a comment. It's important to note that comments are associated with both a position on the Replay and a timestamp. In the image below, you can see that comments are added to the scrubber at the bottom, and clicking on a comment in the sidebar or the comment icon in the scrubber will bring you back to that place and time.
Comments added from the DevTools panel will also show up on the Viewer panel. You can see an example Replay here with a comment identifying an issue from the viewer and a follow up identifying the bug from the code.