The combination of iodoplumbate with xanthene dye (Rhodamine B, RhB) gives rise to a new hybrid [(RhB)(PbI3)(DMF)]n (1, DMF = N,N′-dimethylformamide), which was synthesized using solution method. The (PbI3)nn− chain is constructed from face-sharing PbI6 octahedra. The major central xanthene plane in RhB is twisted with the dihedral angle between two benzene rings of 10.08°, which might be driven by the strong C–H···I hydrogen bonds and C–H···π interactions between two moieties. Driven by these strong non-covalent interactions, broader adsorption zone, distinct dual fluorescence with warm white emission and high photocurrent response can be detected, which was further explained by theoretical calculation.