Highly effective formation of cyclopentanol through the liquid-phase hydration of cyclopentene has been attempted on various zeolites catalysts. MCM-22 zeolite was the most selective catalyst, which actively converted cyclopentene to cyclopentanol with a selectivity up to 99%. The effects on the hydration of catalyst preparation method, reaction atmosphere and temperature have been investigated for the MCM-22 catalysts. On the basis of the effect of reaction atmosphere, the mechanism of liquid-phase cyclopentene hydration was proposed. The thermodynamic equilibrium between cyclopentene and cyclopentanol was suggested to control greatly the cyclopentene conversion. The cyclopentene conversion was increased to 10% by increasing the water/cyclopentene ratio. Poisoning using organic amines with different molecular sizes revealed that the hydration occurred mainly in the 10-membered ring channels of MWW structure, which had an elliptic aperture smaller than that of MFI structure, exhibiting a significant shape selectivity by suppressing the etherification cyclopentanol.