Organophosphorous compounds have recently emerged as a powerful class of compounds with widespread applications, such as in bioactive natural products, pharmaceuticals, agrochemicals and organic materials, and as ligands in catalysis. The preparation of these compounds requires synthetic techniques with novel catalytic systems varying from transition metal, photo- and electrochemical catalysis to transformations without metal catalysts. Over the past few decades, the addition of P-H bonds to alkenes, alkynes, arenes, heteroarenes and other unsaturated substrates in hydrophosphination and other related reactions via the above-mentioned catalytic processes has emerged as an atom economical approach to obtain organophosphorus compounds. In most of the catalytic cycles, the P-H bond is cleaved to yield a phosphorus-based radical, which adds onto the unsaturated substrate followed by reduction of the corresponding radical yielding the product.