Clarification with Texture2D.ReadPixels.

Just want to clarify with ReadPixels. I have a plane with a few materials on its surface, and I want to use ReadPixels from a camera (hidden; doesn't show up on-screen) on this plane. Effectively, it'd give me a single image to match the plane.

Is this how to use it? And I wouldn't need Unity Pro? (Note: It's just a snapshot; not actually using it as a Render Texture like the Unity Pro feature.)

No, if you don't read from a rendertexture, then you're reading from what's actually on the screen. Using a rendertexture is the only way to do that with a "hidden" camera.