A serious problem in biomedical applications is the contamination of medical equipment, that increases the risk of medical failure. A longstanding effort is thus dedicated to develop antibacterial materials that can withstand bacterial growth. Here, we have developed a new material, namely a polydimethylsiloxane (PDMS) and starch bioelastomeric composite that contains an antiseptic compound, namely povidone-iodine (PVPI). The PVPI binds to the bioelastomer via the iodine–starch complexation, only after immersion of the samples in water. Nevertheless, for prolonged water immersion, some PVPI escapes into the water, rendering it yellow. FTIR and μRaman measurements demonstrate the complexation of the iodine to the starch. The sustained release of the PVPI is studied, for different PVPI concentrations, and quantified by UV–vis spectrometry. The antibacterial properties of the material are demonstrated against E. coli, by the agar test. Finally, we performed an experiment adapted from the broth dilution test, normally used for antibiotics, to show the bacteriostatic effect of the PVPI loaded bioelastomers.