H62 brass is subjected to laser shock peening (LSP) with one coverage layer and three coverage layers by high-energy laser beam. Varieties of micro-structure, micro-hardness, and surface roughness before and after LSP are investigated. It is found that the grain size of H62 brass is obviously refined with LSP, and a nanostructure layer is obtained. The micro-hardness and surface roughness of H62 brass increase with the increase of number of LSP coverage layers. The friction and wear test of the as-received sample and LSPed samples (samples subjected to LSP) is carried out by UMT-2 friction and wear test machine. The differences of friction coefficient, wear rate, and wear scar morphology in these samples are analyzed. It is found that under the same friction condition, the friction coefficient and wear rate of LSPed samples are smaller than the as-received sample, which become much smaller with the LSP coverage layers increasing from one to three. It is indicated that LSP can improve the wear resistance of H62 brass, and multi-layer LSP has a better effect on the improvement of the wear resistance of H62 brass. After LSP, the wear mechanism is changed from domination with delamination wear to abrasive wear.