•Determination of arsenic in the sugarcane brandy is important due to high consumption.•Method sensitive involving Cu2+ solutions and a CNTPE containing polymeric resins.•The proposed method is accurate and involves the use of simple, inexpensive reagents.•The results show the potential applicability of the method to real sample analysis.•The method not has drawbacks regarding interference. We have developed an eletroanalytical method that employs Cu2+ solutions to determine arsenic in sugarcane brandy using an electrode consisting of carbon paste modified with carbon nanotubes (CNTPE) and polymeric resins. We used linear sweep (LSV) and differential-pulse (DPV) voltammetry with cathodic stripping for CNTPE containing mineral oil or silicone as binder. The analytical curves were linear from 30 to 110μgL−1 and from 10 to 110μgL−1 for LSV and DPV, respectively. The limits of detection (L.O.D.) and quantification (L.O.Q.) of CNTPE were 10.3 and 34.5μgL−1 for mineral oil and 3.4 and 11.2μgL−1 for silicone. We applied this method to determine arsenic in five commercial sugarcane brandy samples. The results agreed well with those obtained by hydride generation combined with atomic absorption spectrometry (HG AAS).