Liquid core optical fibers can provide very high detectable sensitivity for Raman spectra measurements of liquid samples. Raman spectra by use of liquid core optical fibers and their development are introduced and described. The characteristics and developments of liquid core optical fibers, main intensity considerations in liquid core optical fiber Raman spectroscopy and excitation/collection geometries, and photobleaching and efficient elimination of fluorescence background in liquid core optical fiber Raman spectroscopy are detailedly analysed. The main applications of liquid core optical fibers are especially described in detail. It is of important reference value to the study on Raman spectra measurements of liquid samples using liquid core optical fibers.