In this paper, we experimentally demonstrate femtosecond laser direct writing of conductive structures on the surface of native polydimethylsiloxane (PDMS). Irradiation of femtosecond laser pulses modified the PDMS to black structures, which exhibit electrical conductivity. Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) results show that the black structures were composed of β-silicon carbide (β-SiC), which can be attributed to the pyrolysis of the PDMS. The electrical conductivity was exhibited in limited laser power and scanning speed conditions. The technique we present enables the spatially selective formation of β-SiC on the surface of native PDMS only by irradiation of femtosecond laser pulses. Furthermore, this technique has the potential to open a novel route to simply fabricate flexible/stretchable MEMS devices with SiC microstructures.