The mechanical characteristics of piezoelectric ceramic fibers can be improved by embedding the fibers in a metal matrix. The compressive stress generated during the embedding process, however, limits the polarization of piezoelectric ceramic composites. To study and determine the relationship between the mechanical and piezoelectric properties of piezoelectric ceramics, we analyzed the crystallographic orientation of piezoelectric ceramics embedded in an aluminum matrix via electron backscatter diffraction. The orientation of the crystals before and after the polarization of the piezoelectric fibers, in which residual stresses were generated during embedding, was evaluated. Furthermore, the residual stresses were reduced by heat treatment, and the resultant angle of orientation was evaluated before and after polarization. Results showed that, as the residual stresses were relieved, the orientation of the piezoelectric ceramic crystals changed to reveal increased polarization. Our analysis shows that the crystal orientation of piezoelectric ceramics is impacted by the residual compressive stress that arises from embedding the piezoelectric fiber in the aluminum matrix; it also illustrates the hindering effect of residual stress on the polarization of piezoelectric ceramics.