Hydrothermal syntheses and crystal structures of two zeolite related materials with novel framework topologies are reported. UCSB-4 and UCSB-5 were prepared as cobalt aluminophosphates with N,N,Nβ,Nβ-tetramethylethylenediamine and 1,3-diaminopropane as structure-directing agents, respectively. UCSB-4 has two-dimensional eight-ring channels, whereas UCSB-5 has one-dimensional 10-ring channels. Aluminum and cobalt are not uniformly distributed among framework metal atom sites. In UCSB-4, about one third of metal atom sites are cobalt-rich and about two thirds are aluminum-rich, but in UCSB-5, in addition to one third cobalt-rich sites and one third aluminum-rich sites, approximately one third of metal atom sites are almost equally occupied by aluminum and cobalt. The metal atom site selectivity is related to the orientation of amine molecules which can be determined in both structures. Crystal data for [(CH 3 ) 2 NH(CH 2 ) 2 NH(CH 3 ) 2 ][Co 2 Al 4 (PO 4 ) 6 ] ( UCSB-4): space group P2 1 /c, a=9.2398(8) A Λ, b=18.828(2) A Λ, c=9.4714(8) A Λ, b=118.052(1)Β°, V=1454.1(2) A Λ3, Z=2, Mo Ka, l=0.71073 A Λ, 2h max =45Β°, R(F )=10.1% for 186 parameters and 1896 reflections with I>2s(I ). Crystal data for [NH 3 (CH 2 ) 3 NH 3 ] 4 Co 6 Al 6 (PO 4 ) 12 2 β’ H 2 O: space group P2 1 /c, a=19.2140(4) A Λ, b=9.7711(2) A Λ, c=16.3659(3) A Λ, b=110.279(1)Β°, V=2882.11(8) A Λ3, Z=2, Mo Ka, 2h max =50Β°, R(F )=5.92% for 461 parameters and 3463 reflections with I>2s(I ).