Medical devices (MDs) for infusion and enteral and parenteral nutrition are essentially made of plasticized polyvinyl chloride (PVC). The first step in assessing patient exposure to these plasticizers, as well as ensuring that the MDs are free from di(2-ethylhexyl) phthalate (DEHP), consists of identifying and quantifying the plasticizers present and, consequently, determining which ones are likely to migrate into the patient's body. We compared three different extraction methods using 0.1 g of plasticized PVC: Soxhlet extraction in diethyl ether and ethyl acetate, polymer dissolution, and room temperature extraction in different solvents. It was found that simple room temperature chloroform extraction under optimized conditions (30 min, 50 mL) gave the best separation of plasticizers from the PVC matrix, with extraction yields ranging from 92 to 100% for all plasticizers. This result was confirmed by supplemented Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) and gravimetric analyses. The technique was used on eight marketed medical devices and showed that they contained different amounts of plasticizers, ranging from 25 to 36% of the PVC weight. These yields, associated with the individual physicochemical properties of each plasticizer, highlight the need for further migration studies.