In principle, this reductive Kolbe heterocoupling should be amenable by other means of singleelectron reduction. Thus, photoinduced electron transfer was interrogated for the same reactivity (Figure , entries 2-4). Based on the results of three different experiments, this process appears to be exclusively workable under electrochemical conditions, as no observable product or only traces were observed. In one case, exclusive homodimerization of the 1° RAE 38 was observed New methods for the construction of C-C linkages in a modular way from ubiquitous building blocks can immediately simplify the logic of chemical synthesis. Polar bond analysis is routinely taught at the undergraduate level to help guide chemists to make strategic disconnections. Radical retrosynthesis 23 effectively divorces polarity from the analysis and prioritizes simplicity and building block availability. The reductive Kolbe heterodimerization reported herein has been applied to 25 arbitrarily chosen, previously synthesized substrates containing a myriad of functional groups. The simple one-step procedure and wide LEGO-like availability of starting materials makes this protocol promising despite the near-statistical homo/heterocoupling ratio.