In the present paper, we investigate the origin of photoluminescence (PL) and the changes in the optical properties: refractive index and absorption coefficient, in poly(p-cresolformaldeyde) and diazonaphtoquinone thin films irradiated with Xe ions. Films 400 urn thick have been irradiated with 800 keV Xe2+ ions.in a fluence range from 10(13) to 6 x 10(15) Xe cm(-2). The structural modifications were followed by the techniques of nuclear reaction analysis, elastic recoil detection analysis, Rutherford backscattering, Fourier transform infrared and Raman spectroscopies. The PL behavior was characterised with 488 nm excitation wavelength. The pristine films show emission with maxima of the main bands located at 635, 720 and 830 nm. For fluences up to 10(14) Xe cm(-2), the photoluminescence intensity increases with the irradiation fluence. The chain mobility lowering, characterized by the crosslinked structure, explains this behavior in organic systems. Other possible contribution for increasing of PL intensity, at these fluences, is the presence of oxygen trapped in the polymer chains by the dangling bonds. At intermediate and higher fluences, the photoluminescence starts to decrease. At fluences higher than 10(14) Xe cm(-2), irreversible changes of the organic structure occur and they are characterized by large losses of oxygen and hydrogen, transforming the material into amorphous carbon films. The loss of photoluminescent behavior is associated with the light absorption characteristics of the amorphous carbon structure. This conclusion is supported by the observed increase of the refractive indexes and absorption coefficients, obtained in the infrared region, as well as by the Raman results. Also, the effect of irradiation modifying the refractive index in the infrared region suggests the application of these films as waveguide in this region of wavelength. (C) 2007 Published by Elsevier B.V.