Three-dimensional (3D) printing technology is advantageous in the fast prototyping of complex structures, but its utilization in functional material fabrication is still limited due to a lack of activation capability. To fabricate and activate the functional material of electrets, a synchronized 3D printing and corona charging method is presented to prototype and polarize polylactic acid electrets in one step. By upgrading the 3D printer nozzle and incorporating a needle electrode to apply high voltage, parameters such as needle tip distance and applied voltage level were compared and optimized. Under different experimental conditions, the average surface distribution in the center of the samples was −1498.87 V, −1115.73 V, and −814.51 V. Scanning electron microscopy results showed that the electric field contributes to keeping the printed fiber structure straight. The polylactic acid electrets exhibited relatively uniform surface potential distribution on a sufficiently large sample surface. In addition, the average surface potential retention rate was improved by 12.021-fold compared to ordinary corona-charged samples. The above advantages are unique to the 3D-printed and polarized polylactic acid electrets, proving that the proposed method is suitable for quickly prototyping and effectively polarizing the polylactic acid electrets simultaneously.