This paper deals with the role the substrate on the structure of undoped and n-doped polycrystalline silicon (poly-Si) films produced by Low Pressure Chemical Vapour Deposition (LPCVD). The structural and electrical properties of the films deposited on glass, glass covered with molybdenum (Mo), oxidised crystalline silicon and oxidised crystalline silicon covered with Mo were analysed using X-ray diffraction and Spectroscopic Ellipsometry, dark conductivity and Hall effect measurements. Undoped poly-Si films deposited over Mo present modifications in the crystalline structure relatively to those deposited on the other substrates. The presence of Mo changes the preferential growth orientation, enhancing the Si {111} grains orientation, leading to more compact films. The electrical measurements also confirm that the films grown on Mo substrates present better characteristics. Some differences are also observed during the initial growth stages when using glass or oxidised silicon. Very thin n-doped films present a less effective doping effect when deposited on oxidised silicon than the ones deposited on glass substrates.