Four new organically templated molybdenum compounds, (C 4 H 12 N 2 )[MoO 2 (H 2 AsO 4 ) (AsO 4 )] (1), (C 4 4), have been prepared under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction and thermogravimetric (TG) analysis.All four structures are one-dimensional and contain diprotonated amine cations. The first three compounds are the first organically templated chain structures in the Mo VI /X/O (X ) As, P) lattices; 3 and 4 are the first inorganic-organic mixed anion materials in the molybdenum arsenate and phosphate systems, respectively. Crystal data: 1, monoclinic, P2 1 /n, a )13.4544(8) Å, b ) 6.5648(4) Å, c ) 14.6312(8) Å, β ) 107.522(1)°, Z ) 4; 2, triclinic, P-1, a ) 6.4249(3) Å, b ) 8.6860(4) Å, c ) 12.4506(6) Å, R ) 80.539(1)°, β ) 75.140(1)°, γ ) 70.161(1)°, Z ) 2; 3, monoclinic, P2 1 /n, a ) 6.4577( 2) Å, b ) 13.0135(3) Å, c ) 15.3606(2) Å, β ) 93.199(1)°, Z ) 4; 4, triclinic, P-1, a ) 8.6384(1) Å, b ) 17.7583(3) Å, c ) 18.1172(3) Å, R ) 97.979(1)°, β ) 102.441(1)°, γ ) 98.830(1)°, Z ) 2. Both crystals of 1 and 2 contain the double [Mo 2 X 2 O 12 (H 2 XO 4 )]∞ ribbon, which can be derived from that of VO(HPO 4 )‚4H 2 O. Introduction of oxalate anions into the reaction results in 3 and 4, which contain unusual [MoAsO 6 (C 2 O 4 )]∞ and [Mo 2 PO 8 (C 2 O 4 ) 2 ]∞ chains, respectively. According to the results of TG and DT analyses, the structural motifs of 1, 3, and 4 are thermally stable up to ∼250 °C.