<p>Titanium dioxide (TiO₂), a widely recognized semiconductor in photocatalysis, photodetection, and photovoltaics, faces persistent challenges in spectral response limitations and carrier recombination kinetics. Traditional optimization strategies (element doping, surface plasmon resonance, heterojunction construction, covalent bonding, and hydrogen-bonding, <i>etc</i>.) broaden spectral responses and enhance charge separation but face persistent challenges: doping-induced defects and structural damage, costly noble metal dependency, heterojunction instability, covalent ligand degradation, and weak non-covalent interfacial coupling. This study proposes a molecular-level electron acceptor-mediated dipole coupling method, that synergistically enhances visible-light harvesting and charge transport through a mild, scalable immersion protocol. By functionalizing rutile TiO₂ nanorods with dimethyl viologen (MV), we achieve broadband photoresponse extending from UV to 730 nm (Δ<i>λ</i> = 300+ nm), 10³-fold conductivity enhancement, and 5250% responsivity improvement at 730 nm, which represents a record in reported molecular-level modified TiO₂ materials and ranks among the best performances achieved to date via various methods. Femtosecond transient absorption (<i>fs</i>-TA) spectroscopy reveals dual mechanisms: (1) a surface charge-transfer complex (CTC) prolonging exciton lifetime by 827 ps, and (2) a long-lived charge-separated state (<InlineEquation ID="IEq1"> <EquationSource Format="TEX">\({\bar \tau} \approx 2.07 \; {\rm ns}\)</EquationSource> <EquationSource Format="MATHML"><math display="block"> <mrow> <mrow> <mover> <mi>τ</mi> <mo stretchy="false">¯</mo> </mover> </mrow> </mrow> <mo>≈</mo> <mn>2.07</mn> <mspace width="thickmathspace" /> <mrow> <mi mathvariant="normal">ns</mi> </mrow> </math></EquationSource> </InlineEquation>) that suppresses recombination. This method opens a new modification route for TiO₂, serving as a valuable supplement to known methods.</p>