Fex Ni100-x thin films were deposited on conductive (Cu) and non-conductive (Pd activated glass) substrate using an electroless, polyol method. The stoichiometry of film composition, as compared to the precursor concentration, strongly depended on the substrate position. When the substrate was immersed in the refluxing solution, Fe-deficient films were deposited. However Fe-rich films were synthesized when the substrates were suspended in the vapor phase above the solution. When the substrate was repeatedly suspended above the solution for a short time after each long immersion in solution (this process was denoted as quenching), the films developed an intermediate range of Fe concentration. The surface microstructure, long range and short range orders of these films revealed that the films were oxidized, and the extent of oxidation depended both on the type of substrate and substrate position.