Organophosphorus chemistry is a very broad and exciting field, with potential opportunities to the researchers involved in multi-disciplinary areas of scientific endeavour including organic, medicinal, pharmaceutical, agricultural and industrial chemistry. Organophosphorus compounds find immense applications in all these fields owing to their inherent physical and biological properties. With the advent of the concept of a ‘green chemistry approach’, synthetic organic chemists have been motivated to develop eco-friendly methodologies for generating phosphorus-functionalized compounds of potential interest, focusing on various aspects of green chemistry principles, and, as a result, considerable progress towards green and sustainable chemistry has been accomplished during the last decade. The present chapter is aimed to offer an overview of such developments in the field of organophosphorus chemistry, highlighting the energy-efficient synthetic protocols reported during the period of 2010–2014.