Quaternary ammonium species such as tetramethylammonium hydroxide (TMAH) are widely used industrial chemicals yet generating recalcitrant alkaline wastewater. We investigate the separation and enrichment of TMAH-laden wastewater by electrodialysis (ED). Three ED architectures were comparatively evaluated: conventional anion-cation-exchange (A-C) membrane pair, A-C with bipolar membrane (BP-A-C), and BP-C configuration. The BP-C configuration enabled the highest TMAH enrichment under sustained current, despite lower current efficiency. In parallel, dilute pH decrease (pH-swing) uniquely occurred in BP-C ED. Under an optimized feed volume ratio and stack voltage of BP-C ED, a repeated fresh-to-dilute followed by concentraterecycle (2-FD/CB-R) achieved recovered TMAH concentrations ~1.9 M (from 84 mM) with reduced process scale and competitive energy consumption. These findings offer a new paradigm for sustainable practices for industrial alkaline wastewater treatment coupled with resource recovery.