Elemental white phosphorous (P4) is a crucial feedstock for the entire phosphorus‐derived chemical industry, serving as a common precursor for the ultimate preparation of high‐grade monophosphorus (P1) fine chemicals. Whereas the corresponding manufacturing processes generally suffer from a deep reliance on hazardous reagents, inputs of immense energy, emissions of toxic pollutants, and the generation of substantial waste, which in turn contributes to negative impacts on the environment. In this context, sustainability and safety concerns maintain a consistent impetus for the urgent overall improvement of phosphorus cycles. In this Concept, we present an overview of the most recent growth in photo‐ and electrochemical synthesis of P1 organo‐compounds from P4 with special emphasis on sustainable features. The key aspects of innovations regarding activation mode and mechanism have been compressively analyzed. A preliminary outlook on the possible development of future direction is provided.