TiB2 coatings were plasma sprayed in air and were studied by XPS. There are five elements in the top surface of the studied coatings, namely, B, C, N, O and Ti. Oxygen pick-up in the coatings results in formation of oxides of boron and titanium. Nitrogen was shown to exist in N-Ti and O-N-Ti in the coating. Depending on the spraying parameters, mono-boride as well as di-boride was also detected in the studied coatings. With careful peak fitting it was shown that oxygen may exist in the coating as dissolved atomic O in addition to as lattice oxygen in the oxide of boron and titanium.