A comparative study worked on crystal morphology and luminescence characteristic by hydrothermal method with mineralizer of 3 mol /L KOH, fill factor of 35%, under the condition of three kinds of mineralizers which included 3 mol /L KOH in sample 1, 3 mol /L KOH and 1 mol /L LiOH in sample 2, 3 mol /L KOH and CaO: Zn ( OH) 2 = 2% (amount of substance percentage). Nonpolar ZnO crystals were synthesized by adding proper proportion of CaO or LiOH,the speed of growth along c-axic was weakened obviously. The obtained ZnO crystals exposed more areas on the positive polar face c { 0001}. meanwhile,it exposed negative polar-c {000},positive pyramidal face + p { 101},negative pyramidal face-p {10} and hexagonal faces m {1010}. Only KOH or LiOH auxiliarily added,the emission spectrum was only visible light,no UV light from band edge transition, indicating that the crystal defects luminous center are numerous. A strong UV band emitting from band edge transition was in luminescent spectrumn of the prepared crystals by adding CaO,which indicated a decrease in defects luminous center.