A new highly efficient photopolymer based on a supramolecular polymer was developed for creating surface relief structures in polymer thin films via a reaction/diffusion mechanism known as photoembossing. The effect of the photoinitiator content, the exposure dose, and developing temperature were investigated and the optimal settings were determined by differential scanning calorimetry (DSC) and confocal microscopy. It was found that a surface relief structure of 2.1 µm could be obtained in a 3 µm thin film, which is more than 2.5 times higher than can be achieved in the conventional polymer/monomer based photopolymer systems