Thermal programmed desorption (TPD) is a powerful technique for materials and catalysts characterization. By analyzing TPD curves, it is possible to calculate important parameters as the desorption activation energy, E- d, that depends on the surface coverage (theta) by a nonlinear polynomial function, ie, Ed theta= n-ary sumation k=0N alpha k1-theta k. The Polanyi-Wigner equation, -d theta dT=A theta beta theta nexp-Ed theta RT, can be used as theoretical basis to calculate this parameter, by a fitting regression procedure starting from experimental TPD data. Different degrees (k) for this polynomial equation and different initial values of the frequency factor A(theta) were considered and discussed to obtain the univocal value of desorption energy. Three different Pt and Co based catalysts, suitable for hydrogenation reactions, have been considered as case studies for the application and validation of the proposed calculation procedure.