A possible application of excimer laser irradiation for the preparation of surface enhanced Raman spectroscopy (SERS) substrate is demonstrated. A polyimide foil of 125 μm thickness was irradiated by 240 pulses of focused ArF excimer laser beam (λ= 193 nm, FWHM = 20 ns). The applied fluence was varied between 40 and 80 mJ/cm2. After laser processing, the sample was coated with 40 nm silver by PLD in order to create a conducting layer required for the SERS application. The SERS activity of the samples was tested by Raman microscopy. The Raman spectra of Rhodamine 6G aqueous solution (c=10−3 mol/dm3) were collected from the patterned and metalized areas. For areas prepared at 40–60 mJ/cm2laser fluences, the measured Raman intensities have shown a linear dependence on the applied laser fluence, while above 60 mJ/cm2saturation was observed. The morphology of the SERS active surface areas was investigated by scanning electron microscopy. Finite element modeling was performed in order to simulate the laser-absorption induced heating of the polyimide foil. The simulation resulted in the temporal and spatial distribution of the estimated temperature in the irradiated polyimide sample, which are important for understanding the structure formation process.