While several general reviews of the applications of sum frequency generation vibrational spectroscopy (SFG) appear in the literature, none have focused specifically on the application of SFG to silicones. The unique and somewhat dichotomous surface properties of silicones, and their ever-increasing use in surface and interface-dependent applications such as lubricants, adhesives, micro-fluidic materials, sensors and matrices or scaffolds for nano-composites, calls for increased fundamental understanding that has motivated the use of SFG analysis. This chapter focuses on the combination of this uniquely surface sensitive tool to study applications using PDMS and other silicone-based materials. Because the interpretation of SFG spectra can be quite complex, many of these examples highlight how SFG can be coupled with complementary techniques to provide a more complete understanding of interfacial effects. Lastly, we conclude by providing a summary of strengths, limitations and potential future opportunities for application of SFG and complementary techniques to silicone-based materials.