Molecular dynamics simulations combined with quantitative atomic displacement analyses were performed to study the deformation behaviors of polycrystalline cementite (Fe3C). At low temperature and large grain size, dislocation glide acts as the preferred deformation mechanism. Due to the limited number of slip systems at low temperature, polycrystalline cementite breaks by forming voids at grain boundaries upon tensile loading. When the temperature rises or the grain size reduces, grain boundary sliding becomes the primary mechanism and plastic deformation is accommodated effectively.