A novel strategy of fast solvent induced assembly is used to synthesize a three-dimensional (3D) nanocomposite of multiwalled carbon nanotubes (MWCNTs) and TiO₂, as the counter electrode (CE) of dye-sensitized solar cells (DSSCs). The structure and morphology studies show that the as-prepared nanocomposite possesses a porous structure, large specific surface area and abundant active sites. Electrochemical impedance spectroscopy and cyclic voltammetry analysis reveal that the developed structure facilitates a fast rate of reduction of I₃⁻ and promotes charge transportation. The DSSCs exhibit a remarkable enhanced power conversion efficiency (PCE) of 7.95%, as compared to 7.38% for the conventional Pt CE, after irradiation under standard conditions (AM 1.5G, 100 mW cm⁻²).