Chemical and physical effects induced by bombardment of nearly monodisperse Poly(methyl methacrylate) (PMMA) with energetic ions (He+) at 200 keV have been studied. Bond scission is the main results of low fluence ion irradiation but, at high fluence there is a regime transition of PMMA from positive tone resist behavior to negative tone. The ion-induced chemical reactions in the macromolecular film give rise to gas evolution and chemical changes in the solid residue. The gas formed during the bombardment has been studied by means of a mass spectrometer, while the solid polymer has been characterized by measuring the molecular weight distribution (MWD) and the absorption coefficient in the Near Infrared (NIR), visible, and ultraviolet regions. X-ray Photoelectron Spectroscopy (XPS) has been performed to learn what happens at the surface of the polymer after bombardment. The main result of these studies is that at fluence higher than 10(13) cm(-2) both chemical and physical effects follow a nonlinear behavior due to the transition from a single-track regime to a track overlap regime. This transition is explained in terms of progressive chemical change of the irradiated polymer from the pristine chemical structure to a new one depleted of the ester pendent groups.