This in vitro study evaluated the diagnostic performance of an alternative electric bioimpedance spectroscopy technique (BIS-STEP) detect questionable occlusal carious lesions. Six specialists carried out the visual (V), radiography (R), and combined (VR) exams of 57 sound or non-cavitated occlusal carious lesion teeth classifying the occlusal surfaces in sound surface (H), enamel caries (EC), and dentinal caries (DC). Measurements were based on the current response to a step voltage excitation (BIS-STEP). A fractional electrical model was used to predict the current response in the time domain and to estimate the model parameters: Rs and Rp (resistive parameters), and C and α (fractional parameters). Histological analysis showed caries prevalence of 33.3% being 15.8% hidden caries. Combined examination obtained the best traditional diagnostic results with specificity = 59.0%, sensitivity = 70.9%, and accuracy = 60.8%. There were statistically significant differences in bioimpedance parameters between the H and EC groups (p = 0.016) and between the H and DC groups (Rs, p = 0.006; Rp, p = 0.022, and α, p = 0.041). Using a suitable threshold for the Rs, we obtained specificity = 60.7%, sensitivity = 77.9%, accuracy = 73.2%, and 100% of detection for deep lesions. It can be concluded that BIS-STEP method could be an important tool to improve the detection and management of occlusal non-cavitated primary caries and pigmented sites.