Development of shale oil and gas has prompted people to think about the occurrence space and occurrence states of residual hydrocarbon in shale. There are three occurrence states of residual hydrocarbon in shale: free, adsorbed and dissolved. The contribution of different state hydrocarbon remains uncertain. The occurrence space for hydrocarbon includes pore and surface. Pore can be divided into macropore, mesopore, micropore; and surface can be distinguished between the external and internal surface. Filling and adsorption of hydrocarbon in/on different spaces vary a lot. Furthermore, characteristics of hydrocarbon and organic matter, and the burial and evolution process could complicate the relationships among hydrocarbon, pore and surface. In summary, research on residual hydrocarbon in shale must focus on occurrence state and space simultaneously. Rock-Eval pyrolysis and organic solvent extraction are effective quantitative methods for residual hydrocarbon evaluation, and calibration of characteristic parameters is of great significance. Union of N2 adsorption, mercury intrusion and EGME adsorption methods could achieve the pore structure characteristics of shale comprehensively. These quantitative evaluation methods are the basis for the research on relationships among hydrocarbon, pore and surface. This paper recommended progressively use of organic solvents and wet chemical oxidation methods which can separate free hydrocarbon, physical adsorption hydrocarbon and chemical bonding hydrocarbon gradually, and then we could establish the relationship among hydrocarbon, pore and surface by the combination of residual hydrocarbon and space quantitative characterization methods. Research on the interactions between hydrocarbon and minerals in molecular level and micro-scale will enrich the relationship among hydrocarbon, pore and surface, and it has great significance for us to understand the occurrence mechanism and flow characteristics of residual hydrocarbon in shale.