It depends on the quality of your local tapwater, and the fish that you keep.
Rain water is exceptionaly soft, it contains no hardness whatsoever but can be acidic (depending on where you live) and is sometimes high in nitrates, especially if collected during a thunderstorm.
Fish such as cichlids who like hard, alkaline water will hate rainwater but softwater, acidic loving fish like many Amazonian species will appreciate the rainwater.
It's still best to use a water conditioner though and maybe have carbon in your filter too.
Tapwater is always harder than rainwater but the actual hardness depends on your area as does the pH and the nitrate content.
If you are in a hard water area and keep hard water fish, then tapwater (conditioned of course) is the better option.