This paper reports the synthesis and structures of two key members, [(18C6)K][Cd(SCN)(3)] (1) and [(18C6)(2)Na-2(H2O)(2)](1/2)[Cd(SCN)(3)] (2), of a new inorganic polymers with organic spacers (IPOS) series with the general formula [H-G][M-L], where the organic cation [H-G](q+) is a host (H)-guest (G) complex such as [(crown ether)-(alkali metal)](+) and the inorganic anion [M-L](q-) is a metal (M)-ligand (L) coordination polymer such as [Cd(SCN)(3)(-)]infinity. 1 and 2 were prepared from 18C6, MSCN, and CdSO4 where M = K+ (for 1) and Na+ (for 2), respectively. 1 crystallizes in an orthorhombic unit cell of Cmc2(1) space group symmetry with lattice parameters a = 14.734(3) Angstrom, b = 15.304(2) Angstrom, c = 10.625(3) Angstrom; V = 2396(1) Angstrom(3), and Z = 4. The structure was refined to R(1) = 2.3% for 878 independent reflections (2 theta less than or equal to 46 degrees) with I > 3 sigma. 2 crystallizes in a monoclinic unit cell of P2(1)/n space group symmetry with lattice parameters a = 10.277(3) Angstrom, b = 10.915(5) Angstrom, c = 22.596(7) Angstrom, beta = 111.48(5)degrees; V = 2359(5) Angstrom(3), and Z = 4.