This work presents our current progress on the rational design and synthesis of aluminophosphates with 2-D layer and 3-D open-framework structures. For the design of theoretical structures, we take two ways, one is using building block construction strategy to construct new 2-D networks and 3-D open frameworks. The other is using computer modeling method to systematically enumerate the theoretical network structures. The templating abilities of various amines in the formation of 2-D network or 3-D open-framework aluminophosphates can be evaluated in terms of nonbonding interaction energies of the guest templates and the host inorganic networks or frameworks. This well assists in the rational synthesis of target materials, with the good examples as 2-D Al 3 P 4 O 3Γ 16 anionic layers, and 3-D Al 4 P 5 O 19 OH 2Γ open frameworks with structures analogous to AlPOΒ±HDA (HDA: 1,6-hexanediamine). On the other hand, 3-D open framework can be rationally assembled by a lower-dimensional chain through incorporation of transition metal cations as illustrated by the successful synthesis of a 3-D open-framework nickel aluminophosphate [NiAlP 2 O 8 ][C 2 N 2 H 9 ].