Shale pore structure characterization is key to shale reservoir evaluation, sweet spot selection, and economic exploitation. It remains a challenge to accurately characterize shale micro-nano pores. Common experimental characterization methods for shale pore systems are listed, and advantages and weaknesses of each method are analyzed. An improved pore structure characterization method for shale is proposed by combining Helium and NMR. The new method does not affect shale samples and has a higher accuracy. The affecting factors for shale pore evolution for shale are also discussed, showing that organic matter content and maturity are key factors in total porosity development. Furthermore, a shale porosityβTOC maturity relationship chart is developed based on the experimental data of shale samples selected from six shale reservoirs. The application of this chart in Well X in the Gulong field of Songliao Basin proves its utility in evaluating shale reservoirs.