Here, we prepared the first series of 3D hybrid iodoplumbates with novel porous frameworks of [Pb8I21]5- directed by transition metal complex (TMC) cationic dyes of [TM(2.2-bipy)3]2+. The microporous materials exhibit outstanding visible light-driven photoelectric properties due to the effective photosensitization of the TMC dyes. The coexistence of stronger face- and weaker corner-shared connecting manners affords the feasibility of tailoring the 3D framework into low-dimensional skeletons, which provide a new structural prototype to modify the semiconducting properties similar to those of classic perovskites.