Using this theory, you should divide your canvas into thirds both horizontally and vertically. (Imagine your viewfinder has a tic-tac-toe board superimposed over it.) The best spot to place your main subject is at one of the intersections of these lines. For example, if you have a dramatic sky, consider filling at least the top 2/3's of your image with sky for emphasis. Never put the horizon dead center, dividing your picture in half, if you can help it. If you're taking a portrait, place the most important element (the eyes) along the top line, with the closest eye to you at the intersecting point.
Of course, in any off-center composition, you'll have empty space to the other side. Try to fill that space (especially near one of the intersections, if possible) with a less important subject. For example, something in the distance to give you a secondary object to satisfy your viewer as their eyes explore the image. Of course, if you want to emphasize isolation, you might leave the distance empty ... or even have the smaller "secondary subject" become your primary object and leave the foreground empty.

Just remember, though, any rule can be broken. Don't limit your creativity just because there's a "rule".
