Liquid crystalline materials display unique properties, which can be exploited in various optoelectronic device applications. The Langmuir-Blodgett (LB) film characteristics of polythiophene model compounds containing phenyl rings linked with azomethine, ester, and alkoxy functional groups poly-4-{[(E)-thiophen-3yl-methylidene]amino}phenyl 4-alkyloxybenzoate (PTAPAB series) and poly-4-alkyloxy phenyl 4-[(E)-thiophen-3-ylmethylidene]amino}benzoate (PAPTAB Series) were explored in this study. The AMI optimized geometries of the aforementioned compounds showed that the films have different type of orientation in space because of the change in the linking functional group. The LB film characteristics were studied by applying the concepts of the failure mechanism in tensile failure. The compression-expansion hysteresis cycle of the LB films at predetermined area per repeat unit was used to study the viscous, elastic, and plastic nature of the films. The results showed that in PAPTAB series compounds, the LB films were more flexible and took less surface energy than its PTAPAB series homologues, which formed into LB films of rigid nature. The LB films of PAPTAB series compounds were of more viscoplastic in nature. The studies suggested that PAPTAB series structures exhibited good thin film forming nature than its PTAPAB series homologues. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 173-182, 2009