Natural Curdlan adopts a right-handed 6(1) triple helix, in which the constituting glucan chains are underpinned with each other by the intermolecular hydrogen bonds. Curdlan can form a stoichiometric complex with polynucleotides [e.g., poly(cytidylic acid), poly(C)]. In this paper, we carried out the MOPAC (semiempirical molecular-orbital package) calculation to examine the molecular structure of the Curdlan/poly(C) complex. The calculation exhibited that two types of hydrogen bonds are formed between the Curdlan and the poly(C); the third nitrogen (N3) in cytosine forms a hydrogen bond with the second OH of one Curdlan chain, and the proton of N4 is interacting with the O2 of another Curdlan chain. In our model, the helix diameter of poly(C) is expanded from 11.0 to 15.3 A upon complexation. Despite such large conformational changes, the 6(1) helix structure of poly(C) was maintained even after the complexation. This fact is complementary to the experimental fact that the complexation does not change the band shape of the circular dichroism of poly(C). The chain length dependence of the reaction enthalpy indicated that the complexation becomes thermodynamically more favorable with the chain length increasing. This feature is also consistent with the experimental data.