Based on hollow In 2 O 3 /In 2 S 3 material, an innovative molecularly imprinted photoelectrochemical (PEC) sensor was developed for sensitive detection of glutathione (GSH). Using nicotinamide as a functional monomer, the GSH template molecule was imprinted on hollow In 2 O 3 /In 2 S 3 material with a large specific surface area, which has better selectivity to GSH. The cavernous structure of the material facilitates the enhanced absorption of visible light due to light scattering and reflection. The heterojunction structure between In 2 O 3 and In 2 S 3 also promotes the rapid separation of electron-hole pairs, which significantly enhance the photocurrent response. The constructed sensor exhibits the detection range from 1 μmol L −1 to100 μmol L −1 with a detection limit of 0.82 μmol L −1 (S/N = 3). Meanwhile, the PEC sensor has excellent stability and selectivity, which provides an innovative idea for the actual detection of GSH. Based on hollow In 2 O 3 /In 2 S 3 material, an innovative molecularly imprinted photoelectrochemical (PEC) sensor was developed for sensitive detection of glutathione (GSH). Using nicotinamide as a functional monomer, the GSH template molecule was imprinted on hollow In 2 O 3 /In 2 S 3 material with a large specific surface area, which has better selectivity to GSH. The PEC sensor simultaneously has excellent stability and selectivity, which provide an innovative idea for the actual detection of GSH. • An enhanced MIP PEC sensor with excellent stability and selectivity was developed for detection of GSH. • In 2 O 3 /In 2 S 3 heterojunctions promotes the rapid separation of electron-hole pairs and significantly enhanced the photocurrent response. • The constructed PEC sensor provided an innovative idea for the practical detection of GSH.