In this work, the lacunary Keggin-type phosphotungstates of [PW9O34]9- (PW9) clusters were loaded onto the g-C3N4 nanosheets (NSs) to synthesize the phosphotungstate clusters-decorated 2D heterojunction photocatalysts by using the electrostatic-force driven self-assembly process. The surface charge polarity of g-C3N4 NSs was changed from a negative to a positive charge through the acidizing treatment. The positively-charged g-C3N4 NSs allowed the negatively-charged PW9 clusters to be adsorbed and deposited onto the g-C3N4 NSs, forming the PW9/g-C3N4 heterojunction NSs. The as-synthesized samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and UV-VIS absorption spectra, respectively. The photocatalytic activity tests indicated that, upon simulated sunlight irradiation, the photocatalytic H2-generation rate of PW9/g-C3N4 heterojunction NSs (~23.8 μmol h−1) was ~3.3 times higher than that of the pure g-C3N4 NSs (~7.3 μmol h−1). The enhanced photocatalytic activity of PW9 cluster-decorated g-C3N4 NSs could be attributed to the enhanced separation process of the photoinduced charge-carriers, due to the Z-scheme-mediate charge transfer behavior across their hetero-interface.