Previous studies involving poly N-vinylcaprolactam (PNVCL) and itaconic acid (IA) have synthesised the hydrogels with the presence of a solvent and a crosslinker, producing chemically crosslinked hydrogel systems. In this study, however, temperature sensitive PNVCL was physically crosslinked with a pH-sensitive comonomer IA through ultraviolet (UV) free-radical polymerization, without the presence of a solvent, to produce hydrogels with dual sensitivity. The attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy indicated successful polymerisation of the hydrogels. The temperature and pH sensitivity of the hydrogels was investigated. The lower critical solution temperature (LCST) of the gels was determined using the UV spectrometry and it was found that the incorporation of IA decreased the LCST. Rheology was conducted to investigate the mechanical and viscoelastic properties of the hydrogels, with results indicating IA that enhances the mechanical properties of the gels. Swelling studies were carried out at ~20 °C and 37 °C in different buffer solutions simulating the gastrointestinal tract (pH 2.2 and pH 6.8). In acidic conditions, the gels showed gradual increase in swelling while remaining structurally intact. While in basic conditions, the gels had a burst in swelling and began to gradually degrade after 30 min. Results were similar for drug release studies. Acetaminophen was incorporated into the hydrogels. Drug dissolution studies were carried out at 37 °C in pH 2.2 and pH 6.8. It was found that <20% of acetaminophen was released from the gels in pH 2.2, whereas the maximum drug released at pH 6.8 was 74%. Cytotoxicity studies also demonstrated the hydrogels to be highly biocompatible. These results indicate that physically crosslinked P(NVCL-IA) gels possess dual pH and temperature sensitive properties, which may be beneficial for biomedical applications such as drug delivery.