Visible light responsive CoTiO3 nanoparticles with average diameter of 100 nm were successfully synthesized by sol-gel method and were firstly applied to catalytic activation of peroxymonosulfate (PMS) for degradation of organic pollutants (Rhodamine B (RhB)). Photocatalytic experiments illustrated that CoTiO3 nanoparticles reveal good photocatalytic activity and excellent ability to activate PMS, the synergistic effect of visible light photocatalysis and sulfate radical generated from activated PMS can degradate RhB efficiently. Besides, CoTiO3 nanoparticles maintain their high photocatalytic and activation efficiency after three times recycling.