Photoembossing is a technique used to create relief structures using a patterned contact photo-mask exposure and a thermal development step. Typically, the photopolymer consists of a polymer binder and a monomer in a 1/1 ratio together with a photo-initiator which results in a solid and non-tacky material at room temperature. Here, new mixtures for photoembossing are presented which are potentially biocompatible. A polymer binder such as poly (methyl methacrylate) with triacrylate monomer and biocompatible photo-initiator Irgacure 369 is used. Photopolymer films produced are successfully embossed with height of relief structures controlled by UV dosage and developing temperature. Furthermore, the photopolymer blend is electrospun to form fibres with diameters of 5 μm which are then photoembossed. The photoembossed fibres showed homogenous reproducible surface textures. Biocompatibility is evaluated by culturing human umbilical vein endothelial cells (HUVECs) on films of this photopolymer blend. The study shows that photoembossing is a feasible method of producing surface texturing on both films and electrospun fibres for tissue engineering applications.