In the present work, 10 to 14 nm titania nanoparticles with high-packing density are synthesized by the soft-template method using a range of cationic surfactants including cetyl trimethylammonium bromide (CTAB), Sodium dodecyl sulfate (SDS), and dodecyl trimethylammonium bromide (DTAB). The synthesized nanoparticles are used as a photoanode material in dye solar cells. Density functional theory (DFT) simulations reproduce our experimental results of charge transfer and strong interaction between the TiO2 and N719. N719-TiO2 complex establishes strong electrostatic bonding through H of the dye with the O of TiO2 surface. Solar cell efficiency of 6.08% with 12.63 mA/cm(2), 793 mV, and 48.5% for short circuit current density, open circuit voltage, and fill factor, respectively, are obtained under 1 sun illumination for the dye-sensitized solar cell (DSSC) using a film of mesoporous TiO2 synthesized from the SDS surfactant. On the other hand, the 21 nm commercial TiO2 powder (P25) device results in 4.60% efficiency under similar conditions. Electrochemical impedance spectroscopic studies show that the SDS device has lesser charge transport resistance than the other devices because of its higher surface area, packing density, and dye loading capacity. Our results show that employing high packing density-based TiO2 nanoparticles represents a commercially viable approach for highly beneficial photoanode development for future DSSC applications.