Accessing high-order multiphoton excited fluorescence (H-MPEF) materials is challenging yet and needs complicated synthesis procedures. In this study, we successfully assembled plasmonic Au nanorods (Au NRs) with multiphoton responsive metal-organic frameworks (MOFs), resulting in a significant several-fold enhancement of H-MPEF. The extent of multiphoton enhancement was found to be strongly dependent on the degree of overlap between the multiphoton excitation wavelength of MOFs and the localized surface plasmon resonance absorbance of Au NRs, indicating the importance of plasmon-induced resonance energy transfer. Besides, plasmon-induced hot electron transfer played a vital role in enhanced multiphoton activity as well. Notably, the optimum H-MPEF enhancement occurs at the second near-infrared (NIR-II) region, which provides a promising platform for fluorescent bioimaging. Our findings provide a feasible and practical method to fabricate optimized H-MPEF materials for biological imaging using tissue-penetrating NIR-II light.