Polymides 3a and 3b with stiff-chains bearing trioxaoctyl or tetraoxaundecyl side chains were synthesized and characterized. The polycondensation was done with pyromellitic anhydride and N,N′-bis(1-imidazolylcarbonyl)-2,5-(1,4,7-trioxaoctyl)- or 2,5-(1,4,7,10-tetraoxaundecyl)-1,4-phenylenediamine (2a or 2b). 3b, being sufficiently soluble, was characterized by 13C NMR spectroscopy. The results of IR and 13C NMR spectroscopy prove the presence of the correct imide structure. In solid state 3a and 3b form layered structures with the side chains being in a disordered state.