A novel electrochemical synthesis via a radical generation pathway is described here for the generation of a quaternary megamer structure from secondary dendrimers. The reaction is rapid and completes in <5 min. We have used lower/higher generation poly(amido)amine (PAMAM) dendrimers with carboxylic acid groups at the terminals. A precise electrocatalytic reaction at >3.5 V activates the carboxylic groups to undergo anodic oxidation (-e-) and produce radical carboxylate anions on the dendrimer surface. The reaction further goes through a decarboxylative elimination. Successive self-assembly creates billions of polydispersed and extremely stable ∼500 nm octahedron nanostructures, which we failed to destroy even by using a 20 kV electron beam. This is a new route for the speedy synthesis of important futuristic materials of well-defined shape. It has applications in building designer organic crystals for solar cells, organic electronics, rapid protein gelation, rapid protein crystallization, etc.