The carbon isotopic series of alkane gases were divided into three types: (1) positive carbon isotopic series: δ13C values increased with increasing carbon numbers among the C1–C4 alkanes, which is a typical characteristic for primary alkane gases; (2) negative carbon isotopic series: δ13C values decreased with increasing carbon numbers among the C1–C4 alkanes; and (3) partial carbon isotopic reversal, which had no increasing or decreasing relationship between the δ13C values and carbon numbers. Negative carbon isotopic series were further divided into primary and secondary origins. The primary is a typical characteristic of abiogenic gases, while the secondary is a result of the secondary alteration imposed on biogenic gases usually observed in over-mature shale gas and coal-derived gas. Previous research has proposed several possible explanations for negative carbon isotopic series of secondary origin, such as secondary cracking, diffusion, and the Rayleigh fractionation of ethane and propane through redox reaction with the participation of transition metal and water at 250–300 °C. After a comparative study, the authors found that the negative carbon isotopic series of secondary origin for both shale gas and coal-derived gas appeared in areas where source rocks (shales) were at an over-mature stage, but not in areas where source rocks (shales) were only at a high-maturity stage. As a result, high maturity (>200 °C) was the main controlling factor for the occurrence of negative carbon isotopic series of secondary origin in thermogenic gases. Within this maturity interval, secondary cracking, diffusion, and Rayleigh fractionation of ethane and propane could happen separately or together.