Nanometer scaled pores are critical to studying gas shale reservoirs. In order to obtain the information of the evolution mechanism of nanoscale pore within lacustrine organic-rich shales, artificially matured shale samples from the Ordos Basin were treated using hydrous pyrolysis experiment. Low-temperature nitrogen adsorption, inductively coupled plasma atomic emission spectrometry (ICP-AES), and field emission scanning electron microscopy (FE-SEM) experiments were used to investigate the nanopore evolution with migration and precipitation of materials. The results show that the pore sizes were distributed from 1.1 to 500 nm, and the overall porosity tends to increase first and then decrease. The micropores and fine mesopores (< 10 nm) increased gradually from the 250 to the 350 °C, calcite appeared dissolution following a small peak of feldspar dissolution at this stage, and the CO2 reaches a partial pressure peak at 350 °C. The micropores, mesopores and macropores increased steeply from the 370 °C to the 450 °C. Organic pores were not developed until 350 °C, and well developed at 370 and 400 °C. Organic pores, intergranular pores of clay and intragranular pores of pyrite were well developed at 370 °C. The cumulative specific surface areas increased at 400 °C caused by the dehydration and transformation reaction of clay minerals. This study could provide a reference for the exploration of shale gas in lacustrine shales with different thermal maturities.