Look for the top rail, the obviously wider and usually flat edge. This is the intended upper edge of the rail. Not all rails have a top rail, and many are symmetrical, so this method does not always work.
Ask a helper to hold a length of chair rail against the wall if there is not an obvious top or bottom to the rail. Ensure that the rail is horizontal and at the desired height above the floor. Rails are usually positioned roughly one-third of the distance from the floor to the ceiling. Step away from the wall and look at the rail. Assess its aesthetics and how well it suits the room. Ask yourself whether it looks good this way up.
Turn the rail around so the top edge is now on the bottom. Step away from it again and decide whether the rail looks better or worse this way round. Select the orientation that looks best since, unless the chair rail has a top rail, there is not definitive top or bottom.