Extra virgin olive oil is a product with high commercial value mainly due to its unique quality and bioactive properties. It is commonly adulterated with other less expensive edible oils, making it necessary to develop and study rapid, cheap, and accurate analytical methods to identify extra virgin olive oil adulteration. In this respect, the current study aims to evaluate the application of electrochemical impedance spectroscopy to identify the adulteration of extra virgin olive oil with canola and sunflower oils. The experimental observations were processed through principal component analysis followed by hierarchical clustering to identify groups of treatments with similar behavior. Results have demonstrated that the approach could successfully classify the non-adulterated samples in a separate cluster in relation to the adulterated samples. An empirical equivalent electrical circuit parameter has suggested that the method is able to identify adulteration with 2% of the adopted edible oils and provided a clear distinction between the two adulterants. Overall, the study demonstrated the feasibility of the technique to identify the adulteration of extra virgin olive oil with the two adulterants. However, further studies are necessary to identify the limit of detection clearly and improve the quantification of adulterants added to the control samples.