Graphite nitride carbon nanosheets have received more and more attention toward the photocatalytic research and applications. Ultrathin g-CN nanosheets with porous structure were synthesized successfully by thermal calcination of melamine supramolecular complexes, which was obtained by pre-treating melamine in nitric acid solution at different concentrations (0.5–2 mol/L). Effects of HNO3 pre-treatment on the microstructure of supramolecular complexes were studied. The characteristics of g-CN nanosheets were investigated by X-ray diffractometry, X-ray photoelectron spectroscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The degradation performance for RhB and water splitting hydrogen production performance were used to evaluate the photocatalytic performances of g-CN nanosheets. The morphology and microstructure of HNO3/melamine supramolecular complexes are different from those of melamine precursor due to the better arrangement of the melamine units. Ultrathin porous g-CN nanosheets which possess a thickness of less than 2 nm were successfully prepared by calcination of melamine pre-treated with 1.0 mol/L nitric acid. The g-CN(1.0) nanosheets possess the highest photocatalytic degradation performance and water splitting hydrogen production performance due to the effective separation of photogenerated carriers and high specific surface area providing a large number of active sites.