This work proposes a method for determination Cu(II) concentrations, based on the formation of a copper-1-nitroso-2-naphthol complex, in the presence of micelles; formed by a triblock copolymer, made up of two blocks of polyethylene oxide (PEO), and one block of polypropylene oxide (PPO). The insoluble copper complexes, are concentrated inside the hydrophobic micelle core; formed by the PPO block. For a solution containing 0.200 mg L−1 Cu(II), the proposed method had a relative standard deviation of 2.0% (n = 3); an absolute error from 0.11 to 0.39 mg L−1; and a linear calibration range, from 0.200 to 0.800 mg L−1. Detection and quantification limits, were 43.1 mg L−1 and 144 mg L−1, respectively. We show that there is excellent agreement, between the results obtained using our novel method; and those obtained using flame atomic absorption spectrometry: In the determination of Cu(II) concentrations, in Brazilian sugar-cane spirits. The proposed method, is the first to apply macromolecular micelle systems, to the determination of copper concentrations; and improves upon the results obtained using molecular surfactants. This method is environmentally friendly (since it does not use any organic solvents for extraction), and the triblock copolymer is biodegradable and non-toxic.