As a non-renewable resource, oil faces increasing demand, and the remaining oil recovery rates in existing oil fields still require improvement. The primary objective of this study is to investigate the impact of pore structure parameters on the distribution and recovery of residual oil after polymer flooding by constructing a digital pore network model. Using this model, the study visualizes the post-flooding state of the model with 3DMAX-9.0 software and employs a range of simulation methods, including a detailed analysis of the pore size, coordination number, pore–throat ratio, and wettability, to quantitatively assess how these parameters affect the residual oil distribution and recovery. The research shows that the change in the distribution of pore sizes leads to a decrease in cluster-shaped residual oil and an increase in columnar residual oil. An increase in the coordination number increases the core permeability and reduces the residual oil; for example, when the coordination number increases from 4.3 to 6, the polymer flooding recovery rate increases from 24.57% to 30.44%. An increase in the pore–throat ratio reduces the permeability and causes more residual oil to remain in the throat; for example, when the pore–throat ratio increases from 3.2 to 6.3, the total recovery rate decreases from 74.34% to 63.72%. When the wettability changes from oil-wet to water-wet, the type of residual oil gradually changes from the difficult-to-drive-out columnar and film-shaped to the more easily recoverable cluster-shaped; for example, when the proportion of water-wet throats increases from 0.1:0.9 to 0.6:0.4, the water flooding recovery rate increases from 35.63% to 51.35%. Both qualitative and quantitative results suggest that the digital pore network model developed in this study effectively predicts the residual oil distribution under different pore structures and provides a crucial basis for optimizing residual oil recovery strategies.