As cropland possess dual carbon effects of emitting and sequestering, giving full attention to its net carbon sequestration is an effective option for mitigating global warming. By analyzing the carbon cycle of a cropland use system, we develop an inventory for measuring the net carbon sequestration, covering four carbon sources, i.e., agricultural materials, rice fields, soils, straw burning, with the crop carbon sequestration considered. Different from conventional studies that have focused on quantity, in this study, we define net carbon sequestration performance of cropland use (NCSPC) as the ratio of actual net carbon sequestration to an optimal value per unit of cropland. We estimate the net carbon sequestration of cropland use, from 2000 to 2019, for the study area consisting of the 13 principal grain-producing provinces in China. Then, global-SBM is applied to measure the provincial NCSPC; furthermore, the Theil index and convergence test are employed to portray the spatiotemporal characteristics and regional divergence. The results show the following: (1) The net carbon sequestration was 3.837 t per hectare of cropland in the principal grain-producing area, of which the sequestration and the emission were 6.343 t and 2.506 t, respectively. The share of emissions, from largest to smallest, was methane from rice paddies, agricultural materials, straw burning, and soil nitrous oxide. Specifically, cropland use in Henan exhibited the strongest net carbon sequestration, whereas in Hunan it was the lowest. (2) The average NCSPC was 0.774 in the principal grain-producing area, indicating that 22.6% of the net carbon sequestration per unit of cropland remained to be explored under the corresponding production technology and input combinations. Temporally, the NCSPC had an annual change rate of −0.30%, displaying a slowly declining trend. Spatially, the NCSPC evolved from a scattered distribution to blocky agglomeration, eventually presenting a decreasing pattern from north to south. (3) First, the total Theil index increased, and then decreased, indicating that the regional disparity of the NCSPC expanded early but shrank later. From 2011 to 2019, inter-regional disparity took up more in the total. Over time, both the whole region and the subregions obeyed the σ convergence. Unlike the benign trends observed in Zones I and II, the NCSPC values of Zone III converged to a low level. This study aims to provide a theoretical base for emission mitigation and sequestration promotion for cropland use.