In this study, we fabricated liquid crystal polymer networks (LCNs) containing a large amount of crosslinker by scanning wave photopolymerization, and examined the effect of crosslinker concentration on molecular alignment behavior. Samples with different crosslinker concentrations were photopolymerized by unidirectionally scanning ultraviolet light, resulting in LCN films with uniaxial molecular alignment. The LCN films obtained from the compositions of only monomer or monomer and crosslinker had mesogens aligned in parallel to the light scanning direction. Moreover, the LCN films with high crosslinker concentrations were able to maintain their initial molecular alignment after repeated heating cycles.