In this paper, we review the development and applications of optofluidics investigated based on the platform of microstructured optical fibers (MOFs) that have miniature air channels along the light propagating direction. The flexibility of the customizable air channels of MOFs provides enough space to implement light-matter interaction, as fluids and light can be guided simultaneously along a single strand of fiber. Different techniques employed to achieve the fluidic inlet/outlet as well as different applications for biochemical analysis are presented. This kind of miniature platform based on MOFs is easy to fabricate, free of lithography, and only needs a tiny volume of the sample. Compared to optofluidics on the chip, no additional waveguide is necessary to guide the light since the core is already designed in MOFs. The measurements of flow rate, refractive index of the filled fluids, and chemical reactions can be carried out based on this platform. Furthermore, it can also demonstrate some physical phenomena. Such devices show good potential and prospects for applications in bio-detection as well as material analysis.