Researchers around the globe have witnessed several breakthroughs in s- and p-block metal chemistry. Over the past few years, several applications in catalysis associated with these main group metals have been established, and owing to their abundance and low cost and they have proved to be essential alternatives to transition metal catalysts. In this review, we present a detailed discussion on the catalytic addition of P-H bonds from various phosphine reagents to multiple bonds of unsaturated substrates for the synthesis of organophosphorus compounds with C-P bonds promoted by various s- and p-block metal catalysts, as published in the last decade. © The Royal Society of Chemistry 2021.