TiO2 with exposed (001) facets/Bi4O5Br2 nanosheets heterojunction (TNS/BOB) was fabricated via hydrothermal and electrostatic self-assembly method, their photocatalytic activity for NO removal was evaluated under simulated solar light irradiation. Through optimizing the content of TNS nanosheets, it was observed that the photo-oxidative NO removal rate of 15% TNS/BOB was up to 54.3%, while that of single component TNS and BOB was only 31.1 and 37.7%, respectively. Through the capturing experiments and ESR measurements, the main active species were identified as •O2－ and •OH in the photocatalytic process. DFT computation results and ESR tests reveal that a Z-type electron transport is formed between TNS and BOB, wherein the photo-induced electrons in TNS combined with the holes in BOB, leading to effectively promote charge separation and depress recombination of photogenerated charge carriers in TNS/BOB. The design principle could provide a new idea for the construction of Z-scheme heterojunction photocatalytic for environmental applications.