This study aims to investigate the effects of raw materials and drying methods on the phytochemical and antioxidant capacities of instant sweet tea powder. Four raw materials of sweet tea leave powders (STUT) were extracted and dried with two methods (freeze-drying and spray-drying). The antioxidant capacity, total phenolic content (TPC), total flavonoid content (TFC), and phlorizin and trilobatin contents of obtained instant sweet tea powders were compared. In addition, the single-factor experiments coupled with response surface methodology were used to study the influences of solvent-to-sample ratio, extraction temperature, extraction time, and their interactions on instant sweet tea yield. Results showed that the optimal conditions for extraction were the solvent-to-sample ratio of 19:1 mL/g, extraction temperature of 88 °C, and extraction time of 30 min. The TPC, TFC, antioxidant capacities, and phloridzin and trilobatin contents of instant sweet teas were higher than those of STUT, and the TPC and TFC of freeze-dried instant sweet teas were higher than those of spray-dried instant sweet teas. Significant correlations were found among TPC, TFC, and antioxidant capacities (p < 0.01). The freeze-dried instant sweet tea produced by young leaves (prepared by oven-drying) showed the highest TPC, TFC, and antioxidant capacities, compared with other raw materials and drying methods.