Herein, intensified electrochemiluminescence (ECL) and photoluminescence (PL) supramolecular anion recognition interactions are demonstrated. A bisindolylpyrrole derivative with a structure containing two indole groups and 2-hexyl-pyrrolo[3,4-]pyrrole-1,3(2,5)-dione, BIPPD, was designed and synthesized to induce the enhanced ECL and PL emission based on hydrogen bonding interactions with the dihydrogen phosphate anion. Remarkably, the ECL quantum efficiency and PL quantum yield were discovered to increase up to 5.5-fold and 1.5-fold, respectively, this anion coordination. Dopant PF was found not to form hydrogen bonds, while HSO doping does slightly with the receptor molecule. There was no enhancement in either ECL or PL in both scenarios, revealing great recognition selectivity of the synthesized BIPPD. Mechanistic studies H NMR, ECL, and PL spectra illustrated that the ECL processes varied in the presence and absence of HPO doping, thus leading to the understanding of enhanced efficiency. The bisindolylpyrrole derivative will find applications in supramolecular and analytical chemistry controlled hydrogen bonding interactions.