A novel electrophoretic method for sensitive determination of nine aldehydes, including formaldehyde (C1), acetaldehyde (C2), propanal (C3), butanal (C4), pentanal (C5), hexanal (C6), glutaradehyde (Gla), 2,3-butanedione (Bud) and methylgloxal (MGo) in food samples, has been developed based on CE with amperometric detection (CE-AD). After being derivatized with an electroactive compound, 2-thiobarbituric acid (TBA), these nine non-electroactive aldehydes were converted to electroactive adducts, and therefore detectable by CE-AD approach. Experimental conditions of derivatization and CE-AD detection were optimized. The proposed method was validated according to International Conference on Harmonization (ICH) requirements, with recovery results ranging from 82.8 to 123.8%. Calibration plots of aliphatic aldehydes were linear (r(2)>= 0.9901) in the concentration range from 0.083 to 15.0 mg/L. The LODs were between 0.008 and 0.074 mg/L. The proposed CE-AD method provides a reliable and sensitive quantitative evaluation for non-electroactive low-molecular-mass monoaldehydes and dialdehydes in real sample matrices by employing relatively simple and inexpensive instrument.