Removing painted baseboard molding may be necessary if you are paneling the walls or installing new carpeting or flooring. You may also want to remove and reuse the baseboards if you are remodeling an older home and want to keep it historically correct.
If you wish to reuse the baseboard moldings you will need to be a bit more careful than if you are going to throw them away and install new ones. If there is a lot of paint on the baseboards, take a box knife with a new blade in it and score the paint between the wall and the baseboard to break it free.
Using a pry bar or wrecking bar with a curved claw, insert the claw end between the baseboard and the wall and pull forward. You just want to move the baseboard enough to loosen it some, about half an inch. Do this the entire length of the board until you reach a natural break in the wood or a corner.
Take the pry bar and then insert the claw end into the space between the baseboard and floor and do just as you did in step 2. Usually by doing this you can wiggle the board free and remove it by hand. Number each board on the back with a pencil as you go around the room so you can remember which order to reinstall them.