Polylactic acid (PLA) has intrigued widespread attention as a biodegradable and environmentally friendly polymer, and recent research has revealed that the use of porous PLA in heat sinks for thermal management materials offers promising development potential. However, the heat transfer performance is closely related to its structure theoretically, whether it is virgin, and how the pore structure affects its heat transfer. Therefore, a novel approach is proposed to address this issue by preparing porous PLA through 3D printing at low complexity and cost, the combustion performance is employed to evaluate the heat transfer indirectly, and the higher burning speed represents higher efficient heat transfer. A new framework is developed to investigate combustion performance and three series of PLA with different pore structures in pore shape, size, and interval are studied by combining experimental tests, respectively. It demonstrates that adjusting the pore structure of PLA significantly alters its combustion performance, evidenced by significant variations in flame growth index, which are 83% better for the 2 mm holes than the largest holes and 71% better for the 2 mm interval than for the sparsest pore structure. Generally, it provides some experimental basis for designing porous thermal management materials; the various pore structures generate different combustion performances, corresponding to various heat transfer.