Azobenzene photoalignment materials are highly effective for liquid crystal alignment with high sensitivity and rewritability. A strong relationship between relative humidity and the alignment quality of a thin layer of azobenzenesulfonic dye has been investigated, where the photoinduced phase retardation, order parameter, and anchoring strength of the alignment layer are influenced dramatically by relative humidity. Our results provide fabrication guidance for the photoalignment process in both display and photonic applications. In addition, an exotic substantial ordering enhancement is observed by increasing the relative humidity without further light illumination, where the self-assembly of the photoaligned material incorporated with water molecules is the underlying reason for the enhanced high ordering (S > 0.8). Based on X-ray diffraction and depolarized optical microscopy observation, together with the photoalignment quality, a semicrystalline structure of the humidified azobenzenesulfonic material is proposed. The transition from amorphous solid at low relative humidity to semicrystal at high relative humidity provides a new perspective of understanding the hydrophilic photoalignment materials.