The preparation of polystyrene/thermoplastic starch (PS/TPS) blends was divided into three stages. The first stage involved the preparation of TPS from sago starch. Then, for the second stage, PS was blended with TPS to produce a TPS/PS blend. The ratios of the TPS/PS blend were 20:80, 40:60, 60:40, and 80:20. The final stage was a modification of the composition of TPS/PS blends with succinic anhydride and ascorbic acid treatment. Both untreated and treated blends were characterized by their physical, thermal, and surface morphology properties. The obtained results indicate that modified blends have better tensile strength as the adhesion between TPS and PS was improved. This can be observed from SEM micrographs, as modified blends with succinic anhydride and ascorbic acid had smaller TPS dispersion in PS/TPS blends. The micrograph showed that there was no agglomeration and void formation in the TPS/PS blending process. Furthermore, modified blends show better thermal stability, as proved by thermogravimetric analysis. Water uptake into the TPS/PS blends also decreased after the modifications, and the structural analysis showed the formation of a new peak after the modification process.