The early Cambrian black shale sequence in Northwestern Hunan Province has been investigated for its stable isotopic geochemistry of organic carbon and pyrite sulfur. The relatively low δ 13C values of organic matter, -29.7‰～-34.2‰, are interpreted as caused by the high CO2 concentration in atmosphere/ocean and an anoxic depositional environment in early Cambrian. Variable, but significantly positive δ 34S values, +10.2‰～+28.2‰, for sedimentary pyrite reveals bacterial sulfate reduction as the pyrite-forming process but under sulfate-limited conditions. A protected anoxic basin, which had very limited access to open ocean, and its sediments, where metabolizable organic matter was rich and bioturbation was absent, are supposed to be the sulfate-limited environments and might have existed in South China in the early Cambrian.