In this study, derivatives of polyvinyl alcohol (PVA) grafted with phthalic anhydride (PhA) and dyes were prepared to produce polymeric materials of PVA-g-PhA, PVA-g-PhA-anthocyanin, PVA-g-PhA-bromophenol blue, and PVA-g-PhAthymol blue. The materials were characterised by FTIR and 1 H NMR spectroscopies. The crystallinity of the polymers was evaluated with powder X-ray difraction, and the thermal stability by thermogravimetric analysis (TGA). The synthetic procedure for the polymeric materials entailed the formation of esters. The FTIR spectra of the polymers confrmed their formation since the ester carbonyl group stretch was observed at approximately 1691–1716  cm−1 in each material. NMR spectroscopy confrmed the addition of the dyes to the PVA-g-PhA backbone. All the powder X-ray difractograms displayed the characteristic peak for PVA at a 2θ value of approximately 20°, as well as a small peak at 42° indicative of the semicrystalline nature of the samples. These difractograms indicate a small degree of crystallinity in a mainly bulk amorphous phase. Adding dyes to PVA-g-PhA improved the thermal stability of the resulting polymers. The PVA-g-PhA-bromophenol blue material was the most thermally stable. The absorption properties of PVA-g-PhA were extended into the visible region by the attachment of the dyes. The photostability of the polymers was investigated by irradiating them with 254 nm light. The absorbance of the parent material, PVA-g-PhA, and the anthocyanin derivative increased with irradiation time until it reached a photostationary state. This increase in absorbance is attributed to the formation of more conjugated structures or light-absorbing photoproducts. On the other hand, the PVA-g-PhA-bromophenol blue and PVA-g-PhA-thymol blue materials photodegraded with increasing irradiation time. This research has shown that grafting dyes onto PVA can improve thermal stability and extend light absorption into the visible region. In particular, the addition of anthocyanin dye improved the photostability of the resulting material.