Visible-transparent photoaddressable copolymers are promising material platforms for optical Fourier volumes (OFVs) in waveguide augmented reality (AR) displays. To address strong 400–500 nm absorption in azobenzene systems, we synthesized copolymer films incorporating an N-benzylideneaniline (NBA)-derived photoresponsive unit via ATRP, maintaining visible transparency while enabling polarization-driven, axis-selective photoisomerization. Optical absorption was evaluated by UV–Vis spectroscopy, and OFVs were patterned using 405 nm polarization interference patterning (PIP). The grating-formation window was mapped versus PNBA content and film thickness using polarized optical microscopy and Bragg diffraction. Optimized films produced distinct volume gratings, and thicker films showed enhanced angular selectivity. The resulting holographic optical elements exhibited diffraction across RGB wavelengths, supporting their potential for transparent-display holographic optics.