In the current research, basmati rice starch (BRS) has been modified with octenyl succinic anhydride (OSA). The properties of BRS and modified basmati rice starch (MBRS) were evaluated, and subsequently, the effect of their addition to polyvinyl alcohol (PVA) in two different ratios (70/30 and 30/70) to prepare blend films was studied. The degree of substitution of MBRS was 0.00483%, which was found within the permitted range of Food and Drug Administration guidelines. The pH (6.1 vs. 5.8) and viscosity average molecular weight (1.5 × 104 and 1.275 × 104 Da) were found to be lower for MBRS, solubility (11.52 vs. 13.60%), swelling power (11.5 vs. 13.60 g/g), and oil absorption (2.4 vs. 3.2 g/g) capacities were higher. FTIR and XRD studies revealed minor differences in the MBRS spectra owing to the low substitution. The blend films cast with PVA and MBRS showed higher film thickness, hydration characteristics, transparency, and UV-blocking efficiency.