In this article, we report synthesis and characterization of the self-assembly behavior of coilrod-coil molecules, consisting of four biphenyls and a p-terphenyl unit linked together with ether bonds as a rod segment. These molecules contain lateral methyl or ethoxymethyl groups at 2 and 5 positions of the middle benzene ring of p-terphenyl. The self-assembling behavior of these materials was investigated by means of DSC, POM, and SAXS in the bulk state. The results reveal that self-assembling behavior of these molecules is dramatically influenced by a lateral methyl or ethoxymethyl groups in the middle of rod segment. In addition, molecule with PEO (DP = 17) coil chains of identical coil volume fraction to the corresponding molecule connected by PPO (DP = 12) coil chains, shows diverse self-organizing behavior that may result from the parameters of cross-sectional area of coil segment and the steric hindrance at the rod/coil interface. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1007-1014, 2012