The current studies had already revealed the hydrocarbons could migrate from relatively high hydrocarbon potential stratum to shallow groundwater by corrosion emission and extraction emission in karst area and further impact on human health. Then, the comprehensive experiments were used to understand the mechanism and process of hydrocarbon emission as a continuation of a long-term study on original high hydrocarbon groundwater in shallow Triassic aquifer, taking northwest Guizhou, China, as a reference. The results determined water-rock interaction that lead to the hydrocarbon emission into groundwater with salinity acting as the main driving force. Relatively high salinity promotes the rock corrosion and hydrocarbon emission in the study area. The hydrocarbon emission process varied with different strata, as the results show that the hydrocarbon uniformly distributed in T2g3 than that in T1yn4. Furthermore, the stratum with uniformly distributed hydrocarbon would likely contain high hydrocarbon groundwater, as determined by the process of sedimentation. In addition, “corrosion rate estimation method” and “mineral constituent estimation method” were firstly employed to estimate the hydrocarbon concentration in groundwater to date. Compared with the hydrocarbon concentration of local groundwater samples (0 to 0.14 mg L−1), the result of “mineral constituent estimation method” was analogous to measured value of groundwater samples in the area (0.05 to 0.50 mg L−1), indicating the concentration of hydrocarbon could be estimated by mineral constitutions of groundwater, which was related to the concentration of Ca2+ and Mg2+. Based on the methods and theories in this study, the concentration of original hydrocarbon in shallow groundwater could be estimated and help to understand the mechanism of water-rock interaction in shallow aquifer and original high hydrocarbon groundwater strategic assessment.