The photocatalytic decomposition of water to produce hydrogen (H2) is considered to be an effective method to mitigate the influence of greenhouse effect. In this work, NiCo-LDH/g-C3N4 (NCH/SCN) photocatalysts with direct Z-scheme heterojunction for photocatalytic H2 evolution are synthesized by in situ hydrothermal growth method. It is worth mentioning that the optimized NCH/SCN heterojunction with strong light response exhibits the best H2 evolution performance of 3125 μmol·g−1·h−1, and the apparent quantum yield (AQY) reaches 7.35% at 420 nm. Smoke-like g-C3N4 (SCN) prepared by supramolecular self-assembly method shows a wide triazine ring spacing, which improves electron transfer performance and enhances stability. In addition, the porous structure of SCN is conducive to closely binding with flower-like NiCo-LDH (NCH) to construct direct Z-scheme heterojunction. The reduction of electron transport distance and the presence of internal electric field (IEF) in heterojunction promote the separation of photo-generated carriers. At the same time, NCH/SCN still shows good photocatalytic performance after five cyclic experiments. Characterizations such as valence-band spectrum, work function and density of states were used to analyze the energy band and electronic structure of NCH/SCN, the electron migration path and photocatalytic mechanism were also deduced. This study provides useful strategy for constructing Z-scheme heterojunctions between g-C3N4 and layered double hydroxides (LDHs) to improve photocatalytic H2 evolution performance.