Provided are compositions, processes for making, and processes for using neoalkyl polyol esters and triglycerides as plasticizers. In one form, a neoalkylester triglyceride plasticizers can be produced by (i) drying a polyol feedstream; (ii) contacting in a reactor the dried polyol feedstream with a neoacid feedstream under effective temperature, pressure and time to form a neoalkylester plasticizer effluent stream, and (iii) purifying the neoalkylester plasticizer effluent stream to remove unreacted polyol and unreacted neoacid to form a neoalkylester plasticizer. Such plasticizers can be phthalate-free and provide outstanding properties including a suitable melting or pour point, glass transition temperature, low volatility, increased compatibility, increased hydrolytic stability, and excellent low temperature properties in a range of polymeric resins.