Abstract We report two novel 3D porous metal‐organophosphonate metal organic frameworks (MOFs) [{Cu(4, 4’‐bpy) 0.5 (1,4‐NDPA‐H 2 )] ( 1 ), [{Cu 2 (4,4’‐bpy) 0.5 }(1,4‐NDPA)] ( 2 ) and a non‐porous [{Cu(4, 4’‐bpy)}(2,6‐NDPA‐H 2 )] ( 3 ) constructed using the structurally rigid 1,4‐naphthalenediphosphonic acid (1,4‐NDPA‐H 4 ) and 2,6‐naphthalenediphosphonic acid (2,6‐NDPA‐H 4 ). 1 and 2 exhibit high surface areas obtained using the structurally rigid and short aromatic organophosphonate linkers with copper. The compound 1 has been further analyzed by TGA and Quantum Design PPMS vibrating sample magnetometer.