Host–guest photofunctional materials have received much attention recently due to their potential applications in light emitting diodes, polarized emission, and other optoelectronic fields. In this work, we report the encapsulation of a photoactive ruthenium-based complex (4,4′-diphosphonate-2,2′-bipyridine) into the biphenyl-based metal–organic framework (MOF) as a host–guest material toward potential photofunctional applications. The resulting material (denoted as Ru@MOF) presents different two-color blue/red luminescences at the crystal interior and exterior as detected by three-dimensional confocal fluorescence microscopy. Additionally, up-conversion emission and an enhanced photoluminescence lifetime relative to the pristine Ru-based complex can also be observed in this Ru@MOF system. Upon attaching on the rutile TiO2 nanoarray, the Ru@MOF also exhibits alternated photoelectrochemical properties relative to the pristine complex. Moreover, a density functional theoretical calculation was performed on the Ru@MOF structure to provide understanding of the host–guest interactions. Based on the combination of experimental and theoretical studies on the Ru@MOF system, the aim of this work is to deeply investigate how the host–guest materials can present different photofunctionalities and optoelectronic properties compared with those of the individual components, and to give detailed information on the potential host–guest energy/electronic transfer between the MOF and the complex.