Spontaneous combustion of oil shale is very common as a result of long-time exposure to the air in the Fushun West Open-Pit Mine and West Dump. The PAHs in the high-grade oil shale and its spontaneous combustion product were analyzed semiquantitatively by GC-MS in order to investigate their distribution in different states and their potential negative effects on the environment. Totally 57 and 60 PAHs and their alkyl homologues were identified in the two analyzed samples, among which the alkyl derivatives were predominant, taking up to about 65% in the total PAHs. Those low-molecular mass PAHs (3- or 4-ring) were the main compounds in the two samples. Ten of sixteen USEPA priority pollutant PAHs were detected in two samples, of which phenanthrene was the richest whose contents were 6.93% and 15.03%. Based on comparison of analysis results, the amount and contents of PAHs, except for triaromatic steroid group, were higher in the burning oil shale. So it can be determined that the effects caused by spontaneous combustion of oil shale would be more serious and that the effects of the Fushun oil shale and its spontaneous combustion on the environment should not be ignored in the future work.