Poly (lactic acid) (PLA) compounds with castor oil (CO) and epoxidized castor oil (ECO) were produced via formic acid, with levels of 5% CO, 3 and 5% ECO. The contribution of this study lies in the detailed analysis of thermal degradation and degradation kinetics of PLA/CO and PLA/ECO. Chemical changes were evidenced by Fourier transform infrared (FTIR), thermal stability, and degradation kinetics were investigated by thermogravimetric analysis (TGA), using Friedman (FR), Ozawa–Flynn–Wall (OFW), Kissinger–Akahira–Sunose (KAS) and Vyazovkin (VZ) models. Results showed changes in FTIR spectra for PLA/CO and PLA/ECO. For PLA/5%CO and PLA/3%ECO, lower energy bonds formation were observed, resulting in modifications in the involved molecules and presence of CH type bonds in PLA/5%ECO. TGA analysis showed that PLA presented greater thermal stability compared with PLA/CO and PLA/ECO, with T5% = 306°C. The compounds 5% CO, 3 and 5% ECO exhibited lower degradation temperatures (298, 300, and 296°C), compared with PLA, as well as slower decomposition rates. Kinetic modeling using KAS and OFW models proved to be incapable of describing the degradation kinetics of PLA and its compounds. However, FR and VZ were considered adequate, with discrepancies varying between 7% to −4% and 9% to −3%, which showed higher (215, 185, 210, 189 KJ/mol) at α = 0.3 for PLA.