A homologous series of polyimides (PIs) was prepared in N-methyl-2-pyrrolidone (NMP) from 3,3＇,4,4＇biphenyltetracarboxylic dianhydride (BPDA) and alpha,omega-diaminoalkanes containing 4-10 carbon atoms. For this series the well known odd-even effect was found. Whereas the PIs based on even numbered aliphatic diamines all rapidly crystallize from the melt, the PIs based on 1,7-diaminoheptane (C7) and 1,9-diaminononane (C9) stay amorphous upon cooling from the melt. The chemical structure of the synthesized PIs was confirmed by solid state C-13 n.m.r. and FTi.r. spectroscopy.The PI based on BPDA and 1,8-diaminooctane (DAO) was selected for a study on the relation between chain architecture and crystallization behaviour. This specific polymer was both prepared in NMP and in m-cresol. In NMP the poly(amic acid) intermediate was expected to generate a more branched PI structure than in m-cresol, where this intermediate has never been detected. Furthermore, for both the NMP and the vn-cresol synthesized PI the residual amine endgroups were blocked, since it is known that these endgroups may generate branching and/or crosslinking. The endcapped poly(BPDA-DAO) synthesized in m-cresol exhibited the most optimal crystallization behaviour, which is in line with its expected, predominantly linear character.