A hierarchically ordered 4,4'-biphenylene-bridged mesoporous organosilica framework (Bp-PMO) has been synthesized with the aim of using it as a new hybrid host for Ln(III) ions. A series of novel organic-inorganic luminescent hybrid materials have been obtained by covalently linking Ln(III) complexes (Ln = Eu, Gd, Tb, Er, and Yb) to Bp-PMO functionalized with 2-thenoyltrifluoroacetone (HTTA). The visible and NIR photoluminescence studies of the hybrid materials show that Bp-PMO acts both as an inorganic host and an organic co-sensitizer for Ln(III) ions. The intrinsic quantum yield and lifetime data obtained for the hybrid material containing Eu-III (54.5% and 615 mu s) are among the highest values reported for hybrid materials containing Eu(III)tetrakis(beta-diketonate) complexes. The combination of Bp-PMO and HTTA also provides sizable sensitization for Tb-III, Er-III and Yb-III ions. The overall quantum yields and lifetime measurements for mixed metallic hybrid materials show that Ln -> Ln' energy transfer occurs in the mixed lanthanide systems. In addition, controlling the Ln/Ln' ratio allows one to tune the emission colour.