This study reports the development of nitrogen-doped TiO2 (N–TiO2: N/Ti molar ratio = 1) photocatalyst with the enhanced photoelectronic properties for the phtocatalytic oxidation (PCO) of formaldehyde (FA). The N–TiO2 photocatalyst is coated with ceramic beads and placed in a packed-bed tube reactor to examine the PCO-based mineralization of FA vapor (100 - 500 ppm) under ultraviolet (UV)-A illumination (32 W light source) with the control of flow rate (100–500 mL min−1), O2 (0–21%), and relative humidity (RH: 0–100%). Accordingly, the N-TiO2 in dry conditions showcases 100% degradation of 100 ppm FA with high stability over 5 reuse cycles (compared to the P25 (75.9%) and bare TiO2 (69.2%)) at a flow rate of 100 mL min−1 and a 21 % O2 level (quantum yield = 1.72.E−02 molecules photon−1 and space-time yield = 3.44.E−03 molecules photon−1 mg−1). The superior performance of N–TiO2 may reflect the combination of N/O atoms in the crystal structure to enhance the photo-redox reactivities with the heightened valence band enegry and prolonged lifespan of charge carrier (1.34 ns) relative to 1.04 ns of P25 and 1 ns of pure (anatase) TiO2. The PCO efficiency of N–TiO2 increases by around 1.6 times in slightly humid conditions (74.6%: RH 20%) compared to dry conditions (47%: RH 0%) while the absence of oxygen (at 0% O2) reduces it significantly down to 13.6%. In situ diffuse reflectance infrared Fourier transform spectroscopy and electron paramagnetic resonance studies confirm the critical role of O2 and H2O vapor on the enhanced FA mineralization rate (CO2 yield = 91 %) through the generation of •O2-/•OH oxidative radicals. This study offers deep insights into the practical utility of N–TiO2 for the photocatalytic mineralization of aldehyde VOCs.