Halide perovskite single-crystals have recently been widely highlighted to possess high light harvesting capability and superior charge transport behaviour, which further enable their attractive performance in photovoltaics. However, their application in photoelectrochemical cells has not yet been reported. Here, a methylammonium lead bromide MAPbBr3 single-crystal thin film is reported as a photoanode with potential application in photoelectrochemical organic synthesis, 2,5-dimethoxy-2,5-dihydrofuran. Depositing an ultrathin Al2O3 layer is found to effectively passivate perovskite surface defects. Thus, the nearly 5-fold increase in photoelectrochemical performance with the saturated current being increased from 1.2 to 5.5 mA cm-2 is mainly attributed to suppressed trap-assisted recombination for MAPbBr3 single-crystal thin film/Al2O3. In addition, Ti3+-species-rich titanium deposition has been introduced not only as a protective film but also as a catalytic layer to further advance performance and stability. As an encouraging result, the photoelectrochemical performance and stability of MAPbBr3 single-crystal thin film/Al2O3/Ti-based photoanode have been significantly improved for 6 h continuous dimethoxydihydrofuran evolution test with a high Faraday efficiency of 93%.