Residual bitumen in organic-rich shale of oil windows exists widely, and its effect on the gas storage capacity of shale could be two-fold. Bitumen could occupy and block the nanopores of shale, thereby reducing the gas storage capacity. On the other hand, gas could be dissolved in bitumen in shale gas reservoirs, leading to enhanced gas storage capacity. To quantify the effect of bitumen on the gas-in-place (GIP) estimation of lacustrine organic-rich shale, the micropore characteristics and methane sorption capacity of original and bitumen-free shale from the Triassic Yangchang Formation of the Ordos Basin, combined with the methane dissolution capacity for the isolated bitumen, were analyzed and compared. GIP for the original and bitumen-free shale in the depth range of 500–2500 m was evaluated. The results show that micropores in the shale samples were mainly related to organic matter. Clay mineral-hosted pores contributed slightly to microporosity. Bitumen significantly reduced the micropore surface area and volume of the original shale, with average percentages of 28.09% and 51.26%, respectively. The methane sorption capacity decreased after bitumen removal. When normalized to the original shale mass, the sum of the methane sorption capacity for bitumen-free shale and the methane dissolution capacity for isolated bitumen was similar to the methane sorption capacity of the original shale, indicating that the lack of methane absorbed on bitumen is the main reason for the decrease in methane sorption capacity after bitumen removal. The contribution of absorbed methane on bitumen to sorbed methane in shale could be higher than 36.23%. Dual effects of bitumen on shale GIP were observed. A high content of bitumen (1.12%) increased the GIP of the shale samples, with an average percentage of 23.5% in the depth range of 500–2500 m, while a low content of bitumen (0.06%) decreased the GIP, with an average percentage of 13.6%.