The THz pulses generation of 〈331〉-oriented ZnTe as emitter via its optical rectification were reported. Compared with 〈110〉、〈111〉-oriented ZnTe crystal, the 〈331〉-oriented ZnTe could even emit THz pulse. When the crystal oriented angle was 00 or 1800, the THz pulse amplitude from 〈331〉-oriented could be equal to 〈111〉-oriented, higher than 〈110〉-oriented. The THz pulses detection performance of 〈331〉-oriented ZnTe as detector was calculated via the electro-optical effect. The theoretical calculation from 〈331〉 ZnTe emitter demonstrated a direct way to optimize the working efficiency of a terahertz emitter.