In this paper, the microstructure and microhardness of Ti-6.5Al-3.5Mo-1.5Zr-0.3Si titanium alloy with and without laser shock peening (LSP) were examined and compared. The titanium alloy samples were treated with different layers, at the same power density. X-ray diffraction (XRD), Transmission Electron Microscope (TEM) and microhardness techniques were used to analyse microstructure and mechanical. X-ray diffraction analysis shows that there was not any phase transformation and no new crystalline phases have been formed. TEM studies demonstrate that both α and β phase can been refined in the surface layer with LSP. The microhardness measurements with LSP demonstrate that Hardness of crystallization surface is high up to 418MPa, which is more than the sample without LSP, the shock wave improved the microhardness for about 8%, and the affected depth is about 400 microns from the surface.