This work focuses on the synthesis of heterostructures with compatible band positions and a favourable surface area for the efficient photocatalytic production of molecular hydrogen (H2). In particular, 3-dimensional Nb2O5/g-C3N4 heterostructures with suitable band positions and high surface area have been synthesized employing a hydrothermal method. The combination of a Nb2O5 with a low charge carrier recombination rate and a g-C3N4 exhibiting high visible light absorption resulted in remarkable photocatalytic activity under simulated solar irradiation in the presence of various hole scavengers (triethanolamine (TEOA) and methanol). The following aspects of the novel material have been studied systematically: the influence of different molar ratios of Nb2O5 to g-C3N4 on the heterostructure properties, the role of the employed hole scavengers, and the impact of the co-catalyst and the charge carrier densities affecting the band alignment. The separation/transfer efficiency of the photogenerated electron-hole pairs is found to increase significantly as compared to that of pure Nb2O5 and g-C3N4, respectively, with the highest molecular H2 production of 110 mmol/g·h being obtained for 10 wt % of g-C3N4 over Nb2O5 as compared with that of g-C3N4 (33.46 mmol/g·h) and Nb2O5 (41.20 mmol/g·h). This enhanced photocatalytic activity is attributed to a sufficient interfacial interaction thus favouring the fast photogeneration of electron-hole pairs at the Nb2O5/g-C3N4 interface through a direct Z-scheme.