Carbamazepine is an antiepileptic pharmaceutical which is commonly found in environmental matrices. It passes through wastewater treatment plants (WWTPs) almost completely unaffected and has been found to be highly persistent in the environment. The application of sludge in agricultural fields and the use of WWTP effluents for irrigation constitute a potential source of soil contamination. Consequently, the assessment of the interaction between carbamazepine and soils is of crucial importance to understand its fate in the environment. To monitor the sorption behavior of carbamazepine onto agricultural soils, batch equilibrium experiments were performed using soils subjected to distinct long-term fertilizations. In order to follow the adsorption experiments, an UV spectral deconvolution methodology was applied and the results compared with those from micellar electrokinetic chromatography. The results obtained by both methods did not present significant statistical differences at 95% confidence level. Therefore, it was proven that, in the context of adsorption studies, UV spectral deconvolution is a valid alternative to common chromatographic methods, with the major advantage of being a simple and fast procedure. The adsorption of carbamazepine onto the selected soils was satisfactorily described by the Freundlich model. The obtained Freundlich parameters (K_F) (between 1.79 ± 0.07 and 4.8 ± 0.2 mg kg⁻¹ (mg L⁻¹)^−N) indicate that the adsorption behavior of carbamazepine is dependent on the soil fertilization. Also, it is not extensively sorbed, indicating that carbamazepine present in soils can be a potential source of contamination of surface and ground waters through run-off and infiltration.