D-α-tocopherol polyethylene glycol succinate (TPGS) has good biocompatibility, low immunogenicity, prolonged circulation time, and it can reverse multidrug resistance of tumours. However, the micelle concentration (CMC) of TPGS is too high (0.2 mg/mL) to develop the formulation of the micelle. In this study, TPGS was modified with cholesterol to obtain a new carrier material, TPGS-CHMC. The CMC of TPGS-CHMC was 2 μg/mL, which was extremely lower than that of TPGS. Docetaxel (DTX)-loaded TPGS-CHMC micelles (TPGS-CHMC/DTX) exhibited an average size of approximately 13 nm, a zeta potential of approximately -4.66 mV, and high encapsulation efficiency (99.2 ± 0.6%). TPGS-CHMC reduced mitochondrial membrane potential and cell membrane fluidity in paclitaxel-resistant ovarian cancer cells (A2780/T).