A unified electrochemical decarboxylative strategy for the site-selective construction of carbon-heteroatom bonds is disclosed herein. The metal- and catalyst-free decarboxylation provides access to the functionalization of C- and N-terminus from the simple amino acid feedstock. A wide variety of primary, secondary, and tertiary acids or alcohols were well tolerated. Late-stage functionalization using α-D-galactopyranose, di-peptide, steroid derivatives, and bio-active drug molecules established the robustness and synthesis potential of our approach.