You can use Split Face on any non-family instance. The Split Face tool splits the selected face of the element; it does not change the structure of the element. After splitting the face, you can use the Paint tool to apply a different material to this section of face. See Applying a Material to the Face of an Element.
A wall with a split face (around the window) before painting
A wall with a split face (around the window) after painting
To split a face
In the following example, the wall around the window is split, so that it can be painted to match the border around the door.