Photosensitive polymer hybrids with poly(acrylic acid) (PAA) could be obtained by using caged (photosensitive protecting group modified) alkoxysilane (NVOC-U-PTEOS). Transparent polymer hybrids were prepared with UV irradiation, while the obtained materials were turbid without UV irradiation. This can be attributed to the strong ionic interaction between carboxylic acid groups of PAA and amino groups generated from NVOC-U-PTEOS by photoirradiation. The ionic interaction in polymer hybrids was confirmed utilizing FT-IR and H-1 NMR, and the transparency of the polymer hybrids was evaluated by SEM.