Three spectrophotometric methods were developed for the determination of copper (Cu) in sugar cane spirit using the chromogenic reagents neocuproine, cuprizone, and bathocuproine. Experimental conditions, such as reagent concentration, reducer concentration, pH, buffer concentration, the order of addition of reagents, and the stability of the complexes, were optimized. The work range was established from 1.0 to 10.0 µg/mL, with correlation coefficients of >0.999 for all three optimized methods. The methods were evaluated regarding accuracy by addition and recovery tests at five concentration levels, and the obtained recoveries ranged from 91 to 105% (n = 3). Precision was expressed as RSD (relative standard deviation), with values ranging from 0.01 to 0.17% (n = 10). The method using the chromogenic reagent cuprizone presented the greatest molar absorptivity, followed by bathocuproine and neocuproine. The methods were applied for the determination of Cu in sugar cane spirit, and the results were compared with a reference method by flame atomic absorption spectrometry (FAAS). Calibration curve solutions for FAAS analysis were prepared in a 40% (v/v) alcohol medium in a range of concentrations from 0.5 up to 5 µg/mL. Measurements for Cu determination were carried out at a wavelength of 324.7 nm. The concentrations obtained for Cu in sugar cane spirit samples from Brazil were between 1.99 and 12.63 µg/mL, and about 75% of the samples presented Cu concentrations above the limit established by Brazilian legislation (5.0 µg/mL or 5.0 mg/L).