Details of coupling a catalytic reaction chamber to a liquid nitrogen-cooled cryofocuser/triple quadrupole mass spectrometer for online monitoring of nitric oxide (NO) photocatalytic reaction products are presented. Cryogenic trapping of catalytic reaction products, via cryofocusing prior to mass spectrometry analysis, allows unambiguous characterization of nitrous oxide (N₂O) and nitrogen oxide species (i.e., NO and nitrogen dioxide (NO₂)) at low concentrations. Results are presented, indicating that the major photocatalytic reaction product of NO in the presence of titanium dioxide (TiO₂) P25 and pure anatase catalysts when exposed to ultraviolet (UV) light (at a wavelength of 365 nm) is N₂O. However, in the presence of rutile-rich TiO₂ catalyst and UV light, the conversion of NO to N₂O was less than 5% of that observed with the P25 or pure anatase TiO₂ catalysts.