Nanohybrids of P5W30 CdS with intimate contact have been synthesized via a facile hydrothermal strategy in presence of L-cystine as sulfur precursor, chelating and anchoring linker molecule. In this process, nanosized CdS can be positively-charged by anchoring - NH2 groups in L-cystine structure. Through the electrostatic interaction between the positively-charged amine-functionalized CdS and the negatively-charged Preyssler-type [NaP5W30O110](14-) (denoted as P5W30), P5W30-CdS nanohybrids with intimate contact are achieved, which is verified with XRD, IR, TEM, HRTEM, EDS, XPS and UV-Vis spectra. Of particular importance is that P5W30-CdS nanohybrids demonstrate better photocatalytic performance for H-2 production and RhB degradation than unhybridized CdS and P5W30 under visible light irradiation. The H-2-production activity of CdS is further increased up to 59 times with 8 wt% P5W30 and 0.75 wt% NiS co-loaded, which is attributed to the facilitated charge-transfer between CdS, P5W30 and NiS. The mild, efficient and eco-friendly self-assembly method is versatile and promising for developing photocatalytic hybrid materials. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.