Diffusion coefficients in polymer solutions are strongly dependent on composition and temperature. In many cases sufficient data are not available due to time-consuming measurements and a high number of material systems of interest. In this work a new method is proposed that allows determination of concentration-dependent diffusion coefficients directly from spectroscopic data of single film drying experiments. The quantitative data of concentration profiles in the sample are used to calculate diffusion coefficients by Fick's law. The results are independent of boundary conditions in the gas phase. Two polymer solutions of poly(vinyl acetate) (PVAc) and the solvents methanol and toluene are investigated. The results are compared to diffusion data from the literature. Experimental proof of the independence from boundary conditions is provided. Diffusion coefficients down to values of approximately 10(-14) m(2) s(-1) are accessible. The diffusion data are in good agreement with literature data and suitable for modeling purposes.