The synthesis of pyromellitic diimides (PMDIs) through visible-light-promoted copper-catalyzed reaction of diazo arylidene succinimides has been accomplished without the use of external oxidants. This transformation involves a carbon radical from diazo arylidene succinimides with a copper catalyst or photocatalyst via the proton-coupled electron transfer (PCET) process. This approach successfully challenges a long-standing paradigm in the synthesis of PMDIs. Notably, copper complex (CuNCS) formed in situ proved to be playing a pivotal role to drive the reaction via photoinitiation. Additionally, we synthesized a PMDI molecule known for its prominent aggregation-induced emission (AIE) property. For the very first time, we have synthesized unsymmetrical PMDIs by employing the developed protocol.