Development of synthetic methodologies is essential for research in organic chemistry, medicinal chemistry, and industrial production. Recently, there has been growing demand for the development of novel synthetic methodologies, in which the “novelty” lies not only in achieving the synthesis of complex molecules, but also in high efficiency and environmentally friend process. This demand has given rise to several important research directions, including biocatalysis and electrochemistry, which offer unique mechanisms and potentials of application for organic synthesis, as well as the organophosphorus chemistry, specifically in the stereoselective synthesis of organophosphorus compounds. In this dissertation, we briefly discussed the importance and applications of three research directions: biocatalysis, organophosphorus chemistry, and electrochemistry (Chapter 1), and summarized the recent advances in ene-reductases-catalyzed photoenzymatic reactions, asymmetric synthesis of P(V) compounds, and electrochemical Shono oxidations. In chapter 2, we present a photoenzymatic asymmetric synthesis of tertiary nitroalkanes. The synthesis is achieved by a radical C-alkylation of secondary nitroalkanes catalyzed by ene-reductases. Our methods enabled the synthesis of chiral tertiary nitroalkanes with broad scope, and mechanistic studies suggest the substrates could generate charge-transfer complex in the active site of the enzymes. In chapter 3, we reported a stereoselective synthesis of cyclic P(V) compounds using simple derivatives from L-serine. This method allows the diastereoselective synthesis of a series of oxazaphosphoramides with excellent diastereoselectivity (typically >99:1 dr). Electrochemical decarboxylative reactions was developed for further diversifying the ring structure of the oxazaphosphoramides. More importantly, mechanistic studies showed that the stereoselectivity is generated from two distinct nucleophilic attack pathways on the P(V) centers. In chapter 4, we explored an electrochemical decarboxylative ring-opening cyanation of proline analogues. The reactions started with electrochemical Hofer-Moest reactions of proline-type amino acids to synthesize of N,O acetals, which then reacted with a hydroxylamine-type reagent to afford acyclic nitrile products through a ring opening isomerization. This transformation successfully achieved the “ring-to chain” skeletal remodeling of a series of proline analogues, including several drug molecules fragments. We also applied this type of transformation to N-protected cyclic amine by using electrochemical Shono oxidation.