Summary: A simple method to prepare surfactant‐free and solvent‐free semiconducting polymer particles by using an environmentally benign supercritical carbon dioxide (scCO2) process is reported. The process of the rapid expansion of supercritical solutions (RESS) is used to produce spherical particles of poly[2‐(3‐thienyl)acetyl 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctanoate] (PSFTE), 50–500 nm in size, from 0.1–0.5 wt.‐% PSFTE solutions in CO2 at pre‐expansion temperatures of 40 °C and pre‐expansion pressures of 276 bar.An FESEM image of PSFTE particles produced by the RESS process with CO2.magnified imageAn FESEM image of PSFTE particles produced by the RESS process with CO2.