This study demonstrates a new electrochemical method for rapid determination of ascorbic acid in real samples with electrochemically pretreated screen-printed carbon electrodes. Cyclic voltammetry results indicated that the electrochemically activated electrodes possessed an excellent electrocatalytic activity toward ascorbic acid oxidation and can be successfully used for its selective and sensitive determination in fresh vegetables and fruits. The proposed method was further validated by means of specificity assay with ascorbate oxidase and a comparison with an accurate method such as high-performance liquid chromatography using ultraviolet detection. The electrodes presented the advantages over other existing methods such as mass production and without artificial modification. This study essentially offers a facile and reliable method for rapid determination of ascorbic acid in food analysis with high selectivity and sensitivity as well as low cost.