Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C(12)pda) and dodecylpyridinium (C(12)py) surfactants. The decatungstate (W-10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C(12)pda (C(12)pda-W-10), the heterocyclic moiety directly interacted with W-10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C(12)py (C(12)py-W-10) had similar crystal packing and molecular arrangement to those in the W-10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions.