We have investigated the influence of silver on crystallization and oxygenation or the spin ladder compound La2Cu2O5 (four-leg) single crystals. Large La2Cu2O5 single crystals were successfully grown from charges containing A920 by a self-flux method. Electrical resistivity of the silver grown La2Cu2O5 single crystals (parallel tob-axis) has been found to be about three orders of magnitude lower when compared with the similar crystals grown without silver. Characterizations with optical microscope, XRD, EPMA and HRTEM indicate that the silver does not exist either in free state in the crystal or in the crystal lattice. The results show that the silver facilitates oxygenation in La2Cu2O5 crystals during their growth.