The novel analytical method based on combination of “coffee ring” effect and Surface-enhanced Raman spectroscopy (SERS) has been developed for the speciation of thiolated arsenicals. The gold nanofilm (AuNF) has been fabricated by the coating of glass surface with 3-aminopropyltrimetoxysiloxane (APTMS) and citrate derived negatively charged gold nanoparticles. After the deposition of thioarsenicals buffer solution onto AuNF, following solvent evaporation, ring stamp was formed. Due to the difference in charges of molecules, DMMTA(V) and DMDTA(V) travelled different distances. Overall, the “coffee ring” effect has a decent potential for the speciation of arsenic compounds.