Plasticizers are commonly added to poly(vinyl chloride) (PVC) and other brittle polymers to improve their flexibility and processing properties. Phthalate plasticizers such as di(2-ethylhexyl phthalate) (DEHP) are the most common PVC plasticizers and have recently been linked to a wide range of developmental and reproductive toxicities in mammals. Our group has developed several replacement compounds that have good biodegradation kinetics, low toxicity profiles, and comparable plasticizer properties to DEHP. Knowledge of the rheology of PVC–plasticizer blends at elevated temperatures is crucial for understanding and predicting the behavior of the compounds during processing. In this work, the time–temperature profiles of PVC blended with our replacement green plasticizers—succinates, maleates, and dibenzoates, of varying alkyl chain length—are compared to blends prepared with DEHP and a commercially available non-phthalate plasticizer, di(isononyl cyclohexane-1,2-dicarboxylate) (Hexamoll®
). The relationship between the plasticizer molecular structure and viscoelastic response was examined by applying time–temperature superposition. All compounds except the diethyl esters showed a comparable viscoelastic response to DEHP and Hexamoll®
, and dihexyl succinate exhibited the most effective reduction of the storage modulus G
′. All of the dibenzoate blends exhibited a lower stiffness than the DEHP blends. These experiments help to show that the green plasticizers described herein are viable replacements for DEHP, providing a less toxic alternative with comparable processing and rheological performance.