Photo-embossing has been developed as a convenient and economical method for creating complex surface relief structures in polymer films. The pursuit for large aspect ratios of the photo-embossed structures has never stopped. Here, we demonstrate a simple strategy to obtain improved aspect ratios by adding a quick solvent developing step into the photo-embossing process. A good solvent for the monomer is used to remove unreacted monomers from the unexposed region, resulting in deepened valleys of the surface reliefs. In a polymer film as thin as 2.5 µm, the height of the surface reliefs can be increased by a factor of three to around 1.0 µm. This strategy is also shown to be compatible with other methods used to improve the aspect ratios of the photo-embossed structures. Lastly, we employ these surface relief structures in the fabrication of liquid crystal (LC) devices and investigate their performances for visible light regulation.