© The Royal Society of Chemistry 2020. Laser-based modification of polymer materials has been emerging as a versatile and efficient technique to simultaneously form and pattern electrically conductive materials. Recently, it has been revealed that native polydimethylsiloxane (PDMS) can be modified into electrically conductive structures using femtosecond laser irradiation; however, the details regarding the structures formed by this method have yet to be revealed. In this work, structures were fabricated by focusing and scanning femtosecond laser pulses onto the surface of PDMS. Raman Spectroscopy and Transmission Electron Microscopy (TEM) analyses revealed the formation of silicon carbide (SiC) nanocrystals, as well as multilayer graphitic carbon, in the modified regions of PDMS. The state of the formed material differed depending on the distance from the focal spot, suggesting that photo-thermal effects contributed to the degradation of PDMS into conductive material. Electrical conductivity measurements, in addition to Raman results, indicated that the amount of disorder in the formed graphitic carbon contributes to the electrical conductivity of the fabricated structures.