In this paper, the authors take Huayuan Pb-Zn deposit in Hunan Province and Niujiaotang Pb-Zn deposit in Guizhou Province as examples to discuss the relationship between Pb-Zn deposits and paleo-oil reservoirs in the western Hunan and eastern Guizhou provinces. Influenced by Caledonian Movement, the balance of paleo-oil and ore-forming fluid was destroyed, which attributed to the precipitation of Pb-Zn deposit, and in this process the oilfield brine of the paleo-oil reservoir probably provided Pb-Zn deposits with ore-forming sulfur. The ore-forming time of Pb-Zn deposits is nearly the same as that of the accumulation and destruction of the paleo-oil reservoir during Caledonian.