In the paper, g-C 3 N 4 /MoS 2 materials were prepared by using a one-step calcination method with Na 2 MoO 4 •2H 2 O and thiourea as precursors at different reaction temperatures and reaction rates. With the reaction temperature changing from 500 to 550 °C, the prepared composites were composed with MoS 2 and g-C 3 N 4 nanomaterials, where MoS 2 nanosheets were decorated with g-C 3 N 4 nanoflakes; up to 600 °C, the disappearance of g-C 3 N 4 typical features in FT-IR spectra implies that the composites were mainly consistent with MoS 2 ; further up to 700 °C, XRD patterns and Raman spectra revealed that the composites were composed with MoS 2 nanosheets. All of the prepared samples were used as photocatalysts for hydrogen production, and the highest H 2 production rate of 5.21 mmol•g −1 •h −1 was obtained for sample MC500-2 without a noble metal as a cocatalyst; the sample was prepared at 500 °C with a rate of 2 °C/min. The mechanism behind has been explained with band alignments. UPS and valence spectra revealed that the g-C 3 N 4 /MoS 2 heterostructure in sample MC500-2 is a z-type, which is favorable for the separation of the photogenerated electron−hole pairs. The results will be helpful for the preparation of MoS 2 and g-C 3 N 4 composites and their application in photocatalytic hydrogen production.