Effective photocatalysis processes with production of fewer toxic intermediates are highly desirable for air purification. In this study, titania/hydroxyapatite (TiO₂/HAp) composites were synthesized by a facile hydrothermal method and employed to decontaminate nitric oxide (NO) in air under simulated solar light irradiation for the first time. It was found that the photocatalytic activity of the as-prepared TiO₂/HAp composite (44.61%) was superior to those of the pristine components (TiO₂: 38.57%, HAp: 36.73%) and mechanically mixed samples (35.36%). The TiO₂/HAp composite with mass ratio of 3 : 1 (75% TiO₂/HAp) exhibited the highest NO removal efficiency among them. Moreover, the toxic intermediate NO₂ production was significantly inhibited over TiO₂/HAp. These synergistically improved properties can be ascribed to the high separation efficiency and faster transfer of the photo-generated charge carriers as evidenced by the experimental results from photocurrent tests and electrochemical impedance spectroscopy (EIS). The results from temperature programmed desorption (TPD) confirmed that the 75% TiO₂/HAp sample had stronger chemisorption for NO due to the increased concentration of surface OH groups. Furthermore, the electron spin resonance (ESR) characterization suggested that ˙O₂− and ˙OH radicals were the major species involved for NO removal over TiO₂/HAp composites. The five recycling tests suggested that the TiO₂/HAp has superior photocatalytic stability. This study suggests that the combination of TiO₂ with HAp is an effective approach for air purification. Copyright © 2017 The Royal Society of Chemistry.