Boron-doped amorphous carbon (BDAC) thin films with a regular oxygen reduction reaction (ORR) catalytic activity were synthesized in a hot filament chemical vapor deposition device using a mixture of CH4 and H2 as a gas source and B2O3 as a boron source and then oxidized in air at 380–470 °C for 15–75 min. Scanning electron microscope, transmission electron microscope, Raman spectroscopy, X-ray photoelectron spectroscopy, and electrochemical tests were used to characterize the physical and electrochemical properties of the BDAC catalysts. It was concluded that the BDAC catalyst oxidized at 450 °C for 45 min showed the best ORR catalytic activity in alkaline medium. The oxygen reduction potential and the transfer electron number n, respectively, are − 0.286 V versus Ag/AgCl and 3.24 from the rotating disk electrode experiments. The treated carbon film has better methanol resistance and stability than the commercial Pt/C catalyst.