In this work, the hydrolytic kinetic of piceid was systematically investigated not only in different solvents, but under different conditions of pH and temperature as well. Results showed that the solvents have a significant effect on rate constant. In general, piceid was more readily hydrolyzed in pure organic solvents in which the rate constant was over 10 times of that in conventional aqueous methanol. The solvent effect was analyzed using LSER and it demonstrated that hydrolysis of piceid is accelerated by solvents with larger value of dipolarity/polarizability, being inhibited by hydrogen bond donor solvents. Furthermore, the rate constant increased with elevated acidity and temperature, resulting in shorter time for hydrolysis of piceid and avoiding degradation of resveratrol. The hydrolysis of piceid obeyed first-order kinetics. The new information obtained herein could be helpful to enhanced production of resveratrol via hydrolysis of piceid.