dannysantos also do like that.....
very simple, look for slices of light (morning or evening or noon, doesn't matter, you can get these slices at any time, but when light is directional, i.e. morning or evening higher chance).. this has to do with buildings, etc.
use long focal length, shoot lor... if you want to "bring it out more", use layers and multiply, or selective darkening, that can help. but usually don't need if the light is nice and strong.
nowadays getting more and more common, i didn't even know digitalpimp doing this, i thought dannysantos only. but please, please, make the highlighted person be someone doing something that means something.. not just random people on the street, that will be much more meaningful.