Research on the sustainable livelihoods of rural households is of great significance to mitigating rural poverty and reasonable land expropriation policy helps to realize better livelihoods and sustainable development. Scholars have conducted considerable research on the relationships between land expropriation and farmers' livelihoods. However, few quantitative studies have used the characteristics of villages as control variables to systematically analyze the impact of land expropriation on farmers' livelihood capital and strategy in the mountainous and hilly regions of China. This study uses the Partial Least Squares-Structural Equation Model (PLS- SEM) to systematically explain the impact of land expropriation on farmers' livelihoods in mountainous and hilly regions of Sichuan in 2013, with the characteristics of the village including income, accessibility and terrain as control variables. The analysis uses both representative sample data of 240 rural households and spatial data calculated using a 30 m Digital Elevation Model (DEM) by Geographic Information System (GIS). Results are as follows: (1) The land expropriation characteristics are negatively affected by village accessibility. Villages with worse accessibility tend to have fewer land parcels and less land area expropriated. Additionally, land that is expropriated from inaccessible villages tends to receive less compensation. (2) Natural capital is negatively affected by number and area of land expropriation. Natural capital is not only directly affected by village accessibility, but also indirectly affected by village accessibility through the mediating effect of the number and area of land parcels expropriated. (3) Physical capital is positively affected by compensation for land expropriation, and negatively affected by village accessibility through compensation for land expropriation. The worse a village's accessibility/location is, the less compensation it will receive for land expropriation, resulting in lower physical capital. (4) Financial capital is negatively affected by village accessibility indirectly through compensation for land expropriation. The better the village's accessibility is, the greater is its compensation for land expropriation and, hence, the greater is its financial capital. (5) Social capital is directly and negatively affected by the number and area of land parcels expropriated, and is indirectly and positively affected by village accessibility through the number and area of land parcels expropriated. This study enhances our understanding of the characteristics of land expropriation and rural households' livelihood as well as the impact of land expropriation on rural households' livelihood. These findings provide reference for the formulation of proper policies related to land expropriation and the improvement of rural households' livelihoods in the mountainous and hilly regions of China.