The recent development of open-access optical microcavities opens up a number of intriguing possibilities in the realm of chemical sensing. We provide an overview of the different possible sensing modalities, with examples of refractive index sensing, optical absorption measurements, and optical tracking and trapping of nanoparticles. The extremely small mode volumes within an optical microcavity allow very small numbers of molecules to be probed: our current best detection limits for refractive index and absorption sensing are around 10(5) and 10(2) molecules, respectively, with scope for further improvements in the future.