We report a robust and eco-conscious electrosynthetic protocol for efficiently constructing structurally diverse and biologically relevant dibenzoselenophenes. This transformation proceeds via electrochemical intramolecular C-H activation of bis(biaryl) diselenides, employing LiClO4 as a green electrolyte and tetrabutylammonium bromide as an additive, conducted in DMSO at 70 °C under a constant current of 10 mA using Pt/Pt electrodes. The newly developed method offers several notable advantages, including mild and energy-efficient conditions, transition-metal-free catalysis, short reaction times, high to excellent yields, broad substrate tolerance, scalability to gram-scale synthesis, operational simplicity, and environmental friendliness.