We prepared gadolinium (Gd) ion-modified ZnO nanorods by a sonochemical decomposition of zinc acetate dehydrate and gadolinium acetate hydrate precursor solutions with and without polyethyleneimine (PEI). We investigated the effects of PEI on the sonochemical synthesis of ZnO nanorods with and without Gd ion modifications. In the case of nascent ZnO nanorods, PEI in the precursor solutions can prohibit radial growth but allow axial growth, resulting in changes in the degree of preferred crystal orientations, and in the PL properties of the resulting nanorods. In the case of Gd ion-modified ZnO nanorods, we observed that the ZnO nanorods, fabricated sonochemically in the precursor solutions with PEI, exhibited a peak broadening of the ZnO(002) crystal plane and decreasing crystal orientation with respect to the c plane. We note that PEI can negatively affect the crystal orientation and crystallinity of Gd ion-modified ZnO nanorods, even though it cannot affect the lattice constant.