In this report, a promising solution to the chemoselectivity challenge posed by the strongly oxidative Kolbe reaction is disclosed by using rapid alternating polarity (rAP), a waveform that is implemented on a commercial potentiostat. The rAP-Kolbe reaction features a wide substrate scope, inexpensive and sustainable carbon-based electrodes, operability in both dimerization and heterocoupling modes, and practicality for scale-up applications (Figure . bottom). Testament to the practicality and dramatic cost-savings of this protocol, heretofore costprohibitive building blocks are now easily accessible such as unnatural amino acids and highly coveted polymer building blocks derived from biomass-derived carboxylic acids. As a proof of concept, a unique aciddegradable polymer was constructed from these building blocks. Finally, preliminary mechanistic studies explain why the rAP-Kolbe reaction conquers chemoselectivity constraints and the requirement of platinum-based electrode encountered for over 100 years.