Here, we report an oxygen-tolerant photografting technique to grow polymer brushes employing microliter volumes of monomer solution under ambient conditions. With the key advantages that include spatial control, initiator/catalyst-free nature, and high oxygen tolerance, a series of homo-, multiblock, and arbitrary patterned polymer brushes were successfully obtained by photografting. Moreover, a dual-functional surface with hydrophilic and hydrophobic properties could easily be realized by one-pot photografting. These results illustrated the practicality and versatility of this strategy, which will allow nonexperts access to polymer brush architectures and broaden the potential applications of polymer brushes.