AbstractFour new alicyclic poly{arylene‐9,10‐di[4‐(methyloxy)phenyloxy]‐1,2,3,4,5,6,7,8‐octahydroanthracene‐2,3,6,7‐tetracarboxdiimide}s (APIs) were prepared at 80°C in the presence of NaI in DMSO by the in situ Diels‐Alder polymerization of 1,4‐bis[4‐(methyloxy)phenyloxy]‐2,3,6,7‐tetrakis(bromomethyl)benzene (MPBB) with four arylenebismaleimides (AMIs). The stereochemical isomerisms measured for the model compound DPAI and MDA‐PI by HETCOR spectroscopy and 1H‐NMR spectroscopy, respectively, revealed that DPAI and APIs presumably have only one trans‐bis‐endo‐configuration. Inherent viscosities of APIs varied in the 0.20–0.41 dL/g range. Solubility tests revealed that in spite of the alicyclic units incorporated the APIs were only marginally soluble in polar organic solvents. In TGA in N2 the APIs began to decompose at temperatures higher than 380°C, revealing two‐step pyrolysis behavior. 4‐(Methyloxy)phenyloxy side groups were believed to degrade in the lower temperature range. In DSC and wide‐angle X‐ray diffractometry APIs all appeared completely amorphous and in UV‐Vis spectroscopy both DPAI and APIs were transparent at wavelengths longer than 375 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007