An intervening barrier for photocatalytic water decomposition and pollutant degradation is the frustratingly quick recombination of e(-) h(+) pairs. Delicate design of heterojunction photocatalysts by coupling the semiconductors at nanoscale with well-matched geometrical and electronic alignments is an effective strategy to ameliorate the charge separation. Here a facile and environment-friendly L-cysteine-assisted hydrothermal process under weakly alkaline conditions is demonstrated for the first time to fabricate ZnIn2S4/In(OH)(3) hollow microspheres with intimate contact, which are verified by XRD, SEM, (HR)TEM, XPS, N-2 adsorption-desorption, UVeVis DRS and photoluminescence spectra. ZnIn2S4/In(OH)(3) heterostructure (L-cys/Zn2+ = 4, molar ratio) with a band-gap of 2.50 eV, demonstrates the best photocatalytic performance for water reduction and MB degradation under visible light, outperforming its counterparts (In(OH)(3) and ZnIn2S4). The excellent activity of ZnIn2S4/In(OH)(3) heterostructure arises from the intercrossed band-edge positions as well as the unique hollow structure with large surface area and wide pore-size distribution, which are beneficial for the efficient charge migration from bulk to surface as well as at the interface between ZnIn2S4 and In(OH)(3). This work provides an efficient and eco-friendly strategy for one-pot synthesis of heterostructured composites with intimate contact for photocatalytic application. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.