Vapour phase polymerization of pyrrole on crystalline poly(ethylene oxide) (PEO) complexes gives ordered structure conforming to orthorhombic configuration with lattice parameters of $\text{a = 6.11}\text{A}\text{̊}\text{, b = 7.19}\text{A}\text{̊}\text{and}\text{c = 16.31}\text{A}\text{̊}$. The detailed analysis of these films has been carried out by wide angle X-ray diffraction and X-ray photoelectron spectroscopy. A strong influence of the crystalline substrate is seen in the molecular ordering of the polypyrrole grown on them which can be explained on the basis of lattice mismatch theory. The angular dependence of the C(1s) and N(1s) core level spectra together with their variation with polymerization time suggests a bulk-initiated growth rather than a surface one.