摘要： Multiple-photon photochemical process breaks the existing energy limitation of visible-light photocatalysis. Through careful incorporation of both bis(3,5-dicarboxyphenyl)-pyridine and bis(3,5-dicarboxyphenyl)methylpyridinium ligands into a single metal?organic framework, we reported herein photocatalytic C?N and C?C oxidative coupling reactions that evidenced the direct two-photon response process. Time-dependent luminescence decays studies demonstrated that the framework reached the same excited state by a two-photon absorption process as that reached via a single-photon absorption process, and the excited state could activate substrates even under NIR light irradiation. Under a 660 nm LEDs irradiation, both the photooxidative C?N coupling reaction of benzylamine to form benzylidene-1-phenylmethanamine, and the C?C coupling reaction between nitromethane and N-phenyl-trtrahydroisoquinoline were accelerated directly in a heterogeneous manner. Control experiments suggested that the minimal by-products were formed under the NIR light irradiation comparing to those of the UV light catalytic reactions. Importantly, photon intensity-dependent studies exhibited a nonlinear correlation between catalytic efficiency of MTV-MOFs and photon power intensity, verifying the two-photon responsive nature, which indicated that metal?organic framework with high-density and ordered photoactive motifs could enhance the two-photon absorption ability, thereby improve photocatalytic efficiency even under LEDs irradiation.