Considerable details in the sampling procedure for the detection of the pesticide carbendazim by surface-enhanced Raman scattering (SERS) were developed. Experimental parameters and recommendations were selected to minimize side processes of carbendazim photodestruction as well as to reduce the background signal from the silver substrate. It was found from the comparison of experimental and density functional theory calculations data that the position of the SERS bands in the carbendazim spectrum depends on the nature of the applied solvent due to different orientations of carbendazim with respect to the surface of silver nanoparticle film. Adsorption from a chloroform solution is preferable to form an aqueous solution for SERS because random adsorption of molecules on a silver surface provides robust carbendazim identification, displaying a larger number of bands in the SERS spectrum, a higher “signal-to-noise” ratio, and then the processes of carbendazim photodestruction slow down.