This study demonstrates a cost-effective portable fabrication system for 3D printing complex structures from polydimethylsiloxane (PDMS). Material development and characterisation allowed for the design and production of a 3D printer that is capable of fabricating PDMS structures using a photo-initiator and a LED curing process. A 3D model of a participant’s ear was captured using a handheld scanner. These data were used to directly 3D print an ear. Micro-extrusion direct deposition of PDMS at room temperature is demonstrated via a custom designed 3D printer, with in situ UV cross-linking to facilitate curing of the PDMS during the 3D printing process. This 3D printer has great potential to be used as a fast and facile fabrication approach to create facial and other prosthesis. Future developments will also focus on other application areas such as microfluidics, flexible electronics, and other biomedical applications.