Fractionation of chemical components and hydrogen/carbon isotopic compositions associated with biodegradation of shale gases were determined from typical shale profiles of the Upper Triassic Yanchang Formation, Ordos Basin, China. The results show that the light hydrocarbons (C-1-C-5) of the shale gases were partially degraded by microorganisms and the degradation degree decreased with depth in the profile of Well YY22. However, the degradation degree of Wells FY2 is basically unchanging at different depths and there is no obvious evidence for biodegradation in Well YY18. Biodegradation of C-1 and C-2 can occur and the degradation of hydrocarbon gas does not occur in any obvious sequence, but instead there are only small differences between the relative degradation rates. The relative degradation rates in descending sequence were C-3 = n-C-4 = n-C-5 > i-C-5 = i-C-4 > C-2 > C-1. With intensification of degradation, delta C-13(1) of shale gas showed no obvious change, whereas a marked alteration took place in delta(HC1)-H-2. The delta C-13 values of C-3 and n-C-4 did not alter significantly during early biodegradation; thus, use of exceptional heavy isotopic compositions of those two components to recognize moderate levels of biodegradation is limited. In contrast, the delta C-13 and delta H-2 values of C-2 became more positive even at a low degree of biodegradation; hence, these are effective parameters for identifying biodegraded gases with a low degree of degradation. No obvious change of isotopic composition was observed for the n-C-5 and i-C-5 during degradation. Due to the low relative degradation rates but high content of C-1 and C-2, biodegradation of C-1 and C-2 will severely destroy and decrease the gas content of shale gas. There is a positive relationship between gas content and total organic carbon (TOC) of shale samples without biodegradation. In contrast, samples that have experienced biodegradation show an obvious decrease in gas content with TOC.