Carbon-carbon or carbon-heteroatom bond formation from simple substrates using photoredox-Lewis acid dual catalytic systems is an intriguing area of research. Herein, an expedient photocatalytic strategy for selective C-P bond formation by employing 4CzIPN-Mg(NO3)2·6H2O mediated cooperative catalysis is reported. Following this versatile protocol, various organo-phosphorus compounds like phosphorylated oxindoles, malononitriles, malonates, coumarin esters, and indoles were effectively synthesized. This visible-light-promoted transition-metal-free method originated from the synergistic interaction of 4CzIPN-Mg(NO3)2·6H2O and substrates. Control experiments and other mechanistic studies were carried out to understand this cooperative photocatalytic process.