The response of materials after microscale laser shock peening (μLSP) was experimentally characterized and compared with the theoretical prediction from the finite element method (FEM) analysis in microlength level. X-ray micro-diffraction technique was applied to the post-peened single crystal aluminum of (001) and (110) orientations, and X-ray profile was analyzed by sub-profiling and Fourier analysis method. Spatially resolved residual stress and strain deviation was quantified and explained in terms of the heterogeneous dislocation cell structure. In-plane crystal lattice rotation induced by μLSP was measured by electron backscatter diffraction (EBSD) and compared with the FEM simulation. Average mosaic size was evaluated from X-ray profile Fourier analysis and compared with the result from EBSD. Surface strength increase and dislocation cell structure formation were studied. The systematical characterization will lay the ground work for better understanding the effect of μLSP in microlength level and developing more realistic simulations.