The need of new materials with desirable optical properties has become important in recent years. In particular, a need has emerged for compounds having better luminescence properties in various practical applications. The introduction of rare earth ions as activators improves the luminescence properties of the compounds considerably. Boron is one of the most abundant elements in nature. It readily combines with almost all other elements. In combination with oxygen; it forms borates comprised of various anions such as BO33−, B2O54−, etc. Apart from these simple borates, several complex compositions exist involving mixed anions as well as double metal borates, due to the three‐fold, or four‐fold coordination of borate atoms. Borates intrinsically possesses characteristics that are advantageous for optical materials, which include a wide transparency range, large electronic band gap, good thermal and chemical stability, low preparative temperature, optical stability with good nonlinear characteristics, and an exceptionally high optical damage threshold. The unique crystal structure of borates determines their enhanced ultraviolet light transparency, good nonlinearity, and relatively high resistance against laser‐induced damage. Some of these complex borates have interesting luminescence properties that are covered in this review. These include double borates containing rare earths RM3(BO3)4, pentaborates LaMgB5O10, M3R2(BO3)4, where M is an alkaline earth, mixed anion borates such as aluminoborate SrAl2B2O7, silicate‐borates such as pekovite, SrB2Si2O8, haloborates, M2B5O9X, where M is an alkaline earth and X is a halogen, phosphate borates, and MBPO5, where M is an alkaline earth. Phosphors based on these compositions find use in various applications such as fluorescence lamps, colour TVs, plasma display panels, high‐intensity discharge lamps based on xenon, optically pumped solid‐state lasers, eye‐safe lasers, and X‐ray imaging.