Aldehydes are important compounds in a large number of samples, especially food and beverages. In this work, for the first time, cyclohexane-1,3-dione (CHD) was used as a derivatizing reagent aiming aldehyde (formaldehyde, acetaldehyde, propionaldehyde, and valeraldehyde) analysis by MEKC-DAD. The optimized separation of the derivates was performed using a voltage program (+20 kV, 0-15 min.; +23 kV, 15-17 min.) at a temperature of 26 degrees C, and using as the running buffer a mixture containing 100 mmol/L of sodium dodecyl sulfate and 29 mmol/L of sodium tetraborate at pH 9.2, with maximum absorbance at 260 nm. CHD was compared with two other derivatizing agents: 3-methyl-2-benzothiazolinone hydrazone and phenylhydrazine-4-sulfonic acid. The CHD-aldehyde derivatives were also characterized by LC-MS. The calibration curves for all aldehydes had r(2) above 0.999 and LODs ranged from 0.01 to 0.7 mg/L. The optimized methodology was applied in sugar cane brandy (cachaca) samples successfully. CHD showed to be an alternative derivatization reagent due to its stability, aqueous solubility, high selectivity and sensitivity, reduced impurities, and simple preparation steps.