In a continuation of our earlier reports on new developments in green synthetic approaches in organophosphorus chemistry,¹  the present chapter aims to offer an update on recent key developments in this spectacular field reported in 2020. The topic of green and sustainable chemistry has now attained considerable growth. It has become increasingly popular among researchers working in all branches of chemical science. Dedicated research endeavours have resulted in innumerable green products and processes so far, and such well-documented advances in the fields of green chemistry and green engineering have framed a solid platform for further exploration!²  During the recent past, various greener pathways as alternatives to traditional chemical syntheses and transformations have been invented in diverse fields of chemistry to attain sustainability through newer concepts such as step- and atom-economy and the E-factor. Greener features in designing an alternative protocol for useful organic molecules and/or materials include the use of bio-renewable resources, benign reaction media (use of greener solvents or no solvent), recyclable magnetic heterogeneous catalysts or no catalyst at all, and minimisation of by-products or waste generation with efficient isolation of the target product. Besides, such efforts also focus on energy-efficiency in performing a chemical reaction by careful screening of reaction conditions capable of carrying out the transformation under ambient conditions or by making use of microwaves (MWs), ultrasound (US), visible light, electrochemical cell and mechanical mixing (ball-milling) as green tools for alternative heating and activation of reactants.