A H2/O2 electro-chemical hybrid thruster with a novel design for efficient coupling of hydrogen–oxygen detonation combustion and plasma acceleration is constructed and tested. The comprehensive effects of various parameters, such as the delay time, the background pressure, the capacitance, the external magnetic field, and the propellant mass flow rate, on the performance of the thruster have been explored in single-pulse mode. Several strategies for enhancing the efficiency have been proposed. It is found that, by adding an external magnetic field and decreasing the storage capacitor under the low pressure of 30 Pa and higher single-pulse gas intake at appropriate delay time, the average thrust and efficiency can be enhanced up to 73.2 mN and 15.58%, respectively. In addition, the maximal specific impulse of 676 s is also achieved. The results strongly indicate the great potential of the proposed electro-chemical hybrid thruster in achieving large thrust and high-level specific impulse.