In this work, a novel trimeric octadecyl zwitterionic surfactant (TOCC) was successfully synthesized. TOCC was compounded with sodium salicylate (NaSal) for an optimized formulation to form viscoelastic micelles. The effects of NaSal concentration, pH, and temperature on the rheological properties of TOCC and TOCC/NaSal micelle solutions were investigated. The flow curves for both TOCC and TOCC/NaSal micelle solutions can be fitted with the Carreau–Yasuda model. Zero shear viscosity of TOCC/NaSal micelle solution increased and then decreased with increasing NaSal concentration, and the same trend was observed for viscoelasticity. Some micelle solutions exhibited significant thixotropy with stress overshoot. The optimal composition of the TOCC/NaSal micelle solution obtained was 5.0/0.5 wt%. Frequency sweep in the form of Cole–Cole plots indicated that the viscoelastic modulus of the TOCC/NaSal micelle solution fitted the Maxwell model at low and medium frequencies. With increasing pH, 5.0 wt% TOCC micelle solution had the maximum zero shear viscosity at pH = 6.9. The steady‐state viscosities of different concentrations of TOCC micelle solutions reached their maximum at neutral conditions (pH = 6.5 ~ 7.0). Viscoelastic modulus of 5.0 wt% TOCC and TOCC/NaSal (5.0/0.5 wt%) micelle solutions decreased with increasing temperature, and thermal thixotropy was observed in both micelle solutions. The novel TOCC and TOCC/NaSal micelle solutions enrich the variety of trimeric surfactants and viscoelastic micelle solutions. This study provides a rheological reference for the applications of viscoelastic trimeric surfactants in smart materials and oil fields.