Conformational characteristics, solution (melt) properties, and thermal properties of polyselenoethers [-(CH2)ySe-]x ( y=1, 2, and 3) have been revealed by the rotational isomeric state analysis of ab initio molecular orbital calculations and (1)H and (13)C NMR experiments for monomeric model compounds and compared with those of typical polyethers and polysulfides. The comparative results are summarized here as correlations in conformation among model compounds and unperturbed and crystalline states of the polymers, and thermal properties of the polymer crystals are discussed in terms of intramolecular and intermolecular interactions. By ab initio molecular orbital calculations under periodic boundary conditions, helical structures of poly(methylene oxide), poly(methylene sulfide), and poly(methylene selenide), and the crystal structure of poly(ethylene selenide) have been optimized, and their electronic structures have been predicted. A systematic methodology to predict and characterize up to higher-order structures and various physical properties of polymers incorporated in different phases has been attempted to be developed.