A four-component green tandem approach for the metal-free synthesis of polyfunctionalized dihydro-2-oxypyrroles was devised using the Michael-Mannich cyclocondensation of amines, dialkyl acetylenedicarboxylaes, and formaldehyde. Photo-excited state functions generated from methylene blue (MB+) were employed as single-electron transfer (SET) and energy transfer (EnT) catalysts at ambient temperature in an ethanol solvent, employing visible light as a renewable energy source in the air atmosphere. This study aims to increase the usage of a non-metal cationic dye that is both inexpensive and widely available. Methylene blue is photochemically produced with the least amount of a catalyst due to its high yields, energy-effectiveness, high atom economy, time-saving features of the reaction, and operational simplicity. As a result, a variety of ecological and long-term chemical features are achieved. Surprisingly, such cyclization can be done on a gram scale, implying that the process has industrial potential.