In this review, we examine recent developments in the field of chemical and biological sensing utilizing suspended-core, exposed-core, and hollow-core microstructured optical fibers. Depending on the intended application, a host of sensing modalities have been utilized including labelled fluorescence techniques, and label-free methods such as surface plasmon resonance, fiber Bragg gratings, and Raman scattering. The use of various functionalization techniques adds specificity to both chemical ions and biological molecules. The results shown here highlight some of the important benefits that arise with the use of microstructured optical fibers compared to traditional techniques, including small sample volumes, high sensitivity, and multiplexing.