A simple hydrogenation treatment is used to synthesize unique oxygen-deficient TiO2 with a core/shell structure (TiO2@TiO2-xHx), superior to the high H2-pressure process (under 20 bar for five days). It is demonstrated that oxygen-deficient TiO2 nanoparticle film/Si heterojunction possesses improved photoresponse performance compared to the untreated TiO2 nanoparticle film/Si heterojunction. Particularly, under 900 nm of 0.5 μW cm-2, the oxygen-deficient TiO2 nanoparticle film (TiO2@TiO2-xHx core-shell nanoparticle film)/Si heterojunction shows high responsivity (R) of 336 A W-1, prominent sensitivity (S) of 1.3 × 107 cm2 W-1, accompanied with a fast rise and decay time of 6 and 5 ms, respectively. Significantly, the detectivity (D*) of the photodetector is up to 1.17 × 1014 cm Hz1/2 W-1, which is better than that reported in metal oxide nanomaterials/Si heterojunction photodetectors, and is 4-5 orders of magnitude higher than some 2D nanosheets/Si heterojunctions of 109-1010 cm Hz1/2 W-1, indicating the excellent ability to detect weak signals. The oxygen vacancies generated in amorphous shell TiO2-xHx make the Fermi level of TiO2-x shift near the conduction band minimum and can lead to reduced dark current. The high absorption and reduced dark current of the heterojunction ensure excellent photoresponse properties of oxygen-deficient TiO2 nanoparticle film/Si heterojunction. The H-reduced oxygen-deficient amorphous shell may be an excellent candidate to enhance the photoresponse performance of metal oxide/Si heterojunction.