Stepwise hierarchical and rational synthesis of porous zinc phosphate frameworks by predictable and directed assembly of easily isolable tetrameric zinc phosphate [Zn(dipp)(solv)](4) (dippH(2) = diisopropylphenyldihydrogen phosphate; solv = CH3OH or dimethyl sulfoxide) with D4R (double-4-ring) topology has been achieved. The preformed and highly robust D4R secondary building unit can be coordinatively interconnected through a varied choice of bipyridine-based ditopic spacers L1-L7 to isolate eight functional zinc phosphate frameworks, [Zn-4(dipp)(4)(L1)(1.5)(DMSO)]center dot 4H(2)O (2), [Zn-4(dipp)(4)(L2)(1.5)(CH3OH)] (3), [Zn-4(dipp)(4)(L1)(2)] (4), [Zn-4(dipp)(4)(L3)(2)] (5), [Zn-4(diPP)(4)(L4)(2)] (6), [Zn-4(diPP)(4)(L5)(2)] (7), [Zn-4(diPP)(4)(L6)(2)] (8), and [Zn-4(dipp)(4)(L7)(2)] (9), in good yield. The preparative procedures are simple and do not require high pressure or temperature. Surface area measurements of these framework solids show that the guest accessibility of the frameworks can be tuned by suitable modification of bipyridine spacers.