Bromination of an alkene in presence of water
While there is no formal carbocation intermediate, the cyclic bromonium intermediate has a few different resonance forms (reference):



As you can see on the right, in the structure representing the resonance hybrid, partial positive charges build up on the electrophilic carbons connected to the bromine. The carbon that is more substituted with electron donating groups has a greater partial positive charge (and therefore more electrophilic character) because of the stabilizing effect of the substituents. That's why the nucleophile attacks at the more substituted carbon.