This study presents a polyimide-based optical film in which mismatched charge-transfer complexes (CTCs) are intentionally regulated alongside multiple hydrogen-bonding networks. The resulting film achieved ~90% total transmittance, a yellow index below 3, and a tensile modulus exceeding 10 GPa, which is the best-recorded balance between mechanical strength and optical properties. It also exhibited excellent folding reliability, sustaining more than 500,000 cycles at a radius of 1.5 mm without structural failure. These enhanced properties originate from a unique supramolecular architecture governed by cooperative hydrogen-bonding and salt-complexation interactions, which intensify the CTC framework. Furthermore, a mechanism is proposed to elucidate the origin of CTC intensification and its correlation with the mechanical behavior of the display surface.