As known, the electron transfer behavior in photocatalysis is short-distance transportation, which leads the photo-induced electrons and holes to be localized. The temporarily separated electrons and holes will recombine with each other in the localized region. In this paper, we successfully achieved electron transfer in a homojunction of branched rutile TiO2 nanorod @nanoparticle core-shell architecture by quantum confinement effect aroused by the nanoparticle, which is proved by the blue-shifting in UV-vis absorption spectrum of the homojunction. Meanwhile, an absolute charge separation is also achieved by the long-distance electron transfer along the single-crystalline rutile TiO2 nanorod as uninterrupted high-speed electron transfer channel to FTO substrates. Based on the effective charge separation, the photocatalytic decomposition of gaseous benzene by the homojunction is significantly enhanced, yielding 10 times CO2 than that of the nanorod array. This homojunction interfacial charge separation, aroused by quantum effect, through long-distance transfer along the single-crystalline nanorod gives us inspiration to achieve efficient charge separation with defect-less interfaces, which might can be utilized for real-time environmental abatement and energy generation simultaneously. (C) 2016 Elsevier B.V. All rights reserved.