Rational arrangement of nanosized semiconductor components in the multi-heterojunction photocatalyst can lead to the formation of a high-speed transport channel for charge-carriers separation and migration, which provides a promising way to achieve excellent photocatalytic efficiency for solar fuels generation. Herein, we develop a photo-assisted self-optimization strategy to re-build the charge-carriers transport channel in the copper species nanocrystals/TiO2 electrospun nanofibers with the organic hydrogen-carrier molecules as the photo-reactants. As a result of the dynamics difference of the excitons migration during the photocatalytic process, the binary CuO/TiO2 heterojunction nanofibers are recrystallized to form the quaternary CuiCu(2)O/CuO/TiO2 multi-heterojunction nanofibers that exhibits a higher rate constant (similar to 1.7 x 10(8)S(-1)) for the interfacial electron-transfer than the former nanofibers (similar to 0.7 x 10(8)S(-1)) due to the improved charge-carriers transport channel. In this way, a 40-fold enhanced H-2 generation rate was observed on the recrystallized nanofibers photocatalyst during the photocatalytic decomposition of formic acid as compared to the pure TiO2 nanofibers. Our work presents an available paradigm to skillfully use a transient photo-physicochemical process to mildly engineer a high-quality charge-carriers transport channel in the hetero-nanophotocatalyst for realizing an optimal photocatalytic performance. (C) 2016 Elsevier B.V. All rights reserved.