P(O)–X (X = S, N, O, P) bond-containing compounds have extensive application in medicinal chemistry, agrochemistry, and material chemistry. These useful organophosphorus compounds also have many applications in organic synthesis. In light of the importance of titled compounds, there is continuing interest in the development of synthetic methods for P(O)–X bonds construction. In the last 4 years, the direct coupling reaction of P(O)–H compounds with thiols, alcohols, and amines/amides has received much attention because of the atom-economic character. This review aims to give an overview of new developments in cross-dehydrogenative coupling reactions between P(O)–H and X–H (X = S, N, O, P) bonds, with special emphasis on the mechanistic aspects of the reactions.