Early Cambrian shale is an important petroleum source rock around the world. Because of little drilling data and poor seismic data, until recently, organic matter enrichment of the Lower Cambrian Yuertusi and Xishanbulake formations shale is still an enigma in the Tarim Basin, northwestern China. Total organic carbon (TOC), major and trace element data of Cambrian shale samples from five boreholes have been analyzed to decipher the mechanism of the organic matter enrichment. The results show that the shales deposited in the western restricted intraplatform have much higher TOC contents (3.2%–19.8%, on average 11.0%) than those from the eastern basin (2.2%–10.2%, on average 4.5%). The paleoproductivity proxies (Ba, Ba/Al, P/Al) in the western restricted platform are much higher than those in the eastern basin. The trace element indicators such as V/Cr, Ni/Co, Mo–TOC and MoEF–UEF suggest an anoxic environment across the basin, but a more restricted environment in the western intraplatform. The paleoproductivity rather than anoxic condition and hydrothermal activity are concluded to have resulted in the differentiation of the organic matter enrichment from the western intraplatform to eastern basin in the early Cambrian shales; the restricted environment was favorable for paleoproductivity and preservation of organic matter.