Persistent photoconductivity (PPC) in 30-MeV electron irradiated ZnO single crystals is studied by excitation using light emitting diodes (LEDs) with various wavelengths. The decay transient of the photoconductivity shows relaxation times in the range of a few ten days for the illumination at 90 K and a few hours at room temperature. An electron paramagnetic resonance (EPR) signal with g-value=2.005 appears after illumination of blue LED, suggesting the transfer from the artificially introduced oxygen vacancy of 2+ charge state to the metastable + charge state. Once generated, the metastable state does not immediately decay into the 2+ charge state because of energetic barriers of 190 meV, supporting the mechanism of PPC proposed by Van de Walle.