The self-consistent charge density functional tight binding method was combined with the path-integral molecular dynamics method for the first time to evaluate the two-dimensional free-energy surface including nuclear quantum effects of a proton-transfer reaction in a 2,4-dichlorophenol-trimethylamine complex. A statistically converged two-dimensional quantum free-energy surface was evaluated by the multidimensional blue moon ensemble method. The accuracy was guaranteed by optimizing the repulsive potential between the sp3-hybridized nitrogen and hydrogen atoms in a SCC-DFTB3 parameter set for the system to reproduce high-level quantum chemical calculations. The present study illustrates the usefulness of this new approach to investigate nuclear quantum effects in various realistic proton-transfer reactions.