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Oil spill-induced vapor cloud explosions in a confined space can cause catastrophic consequences. In this work, investigation was conducted on the catastrophic pipeline leak, oil spill, and the resulting vapor cloud explosion accident occurring in China in 2013 by modeling analysis, field surveys, and numerical simulations. The total amount of the spilled oil was up to 2044.4 m3 due to improper disposal. The long residence time of the oil remaining in a confined space permitted the formation of explosive mixtures and caused the vapor cloud explosion. A numerical model was developed to estimate the consequence of the explosion based on volatilization testing results. The results show that the death-leading zone and the glass-breaking zone could be 18 m and 92 m, respectively, which are consistent with the field investigation. The severity of the explosion is related to the amount of the oil spill, properties of oil, and volatilization time. It is recommended that a comprehensive risk assessment be conducted to analyze the possible consequences upon oil spilling into a confined space. Prompt collection and ventilation measures should be taken immediately after the spill occurs to reduce the time for oil volatilization and prevent the mixture from reaching its explosive limit.