A chemical foaming process of polylactic acid (PLA) was developed via the solid-state processing methods of solid-state shear pulverization (SSSP) and cryogenic milling. Based on the ability of solid-state processing to enhance the crystallization kinetics of PLA, chemical foaming agents (CFA) are first compounded before foaming via compression molding. Specifically, the effects of the pre-foaming solid-state processing method and CFA concentration were investigated. Density reduction, mechanical properties, thermal behavior, and cell density of PLA foams are characterized. Solid-state processing of PLA before foaming greatly increases the extent of PLA foaming by achieving void fractions approximately twice that of the control foams. PLA’s improved ability to crystallize is displayed through both dynamic mechanical analysis and differential scanning calorimetry. The solid-state-processed foams display superior mechanical robustness and undergo low stress relaxation. The cell density of the PLA foams also increases with solid-state processing, especially through SSSP. Additionally, crosslinking of PLA during the pre-foaming processing step is found to result in the greatest enhancement of crystallization but decreased void fraction and foam effectiveness. Overall, SSSP and cryogenic milling show significant promise in improving chemical foaming in alternative biopolymers.