The present invention provides a highly selective synthesis method for hypophosphorous acid / phosphorous acid / phosphate derivatives containing different substituted functional groups. In the present invention, base is adopted as a catalyst, compounds containing P(O)-OH and halogenated aliphatic hydrocarbons are adopted as reaction substrates, and an organic solvent is added into the reaction system. The method has advantages that the catalyst is cheap and easily obtained; reaction conditions are mild, safe and reliable; the selectivity of target product is close to 100%, and the yield is up to 90%. According to the present invention, the problems of low reaction selectivity, tedious reaction steps, low yields, needing reagents harmful to environment and the like in conventional methods for synthesizing hypophosphorous acid / phosphorous acid / phosphate compound are solved. The method has good industrial application prospects. The present invention also provides the corresponding hypophosphorous acid / phosphorous acid / phosphate derivatives containing different substituted functional groups.