The objective of this study was to determine the ability of several techniques to detect natural secondary caries adjacent to proximal class II amalgam restorations. Two sites were selected and marked on each of 50 human extracted posterior teeth. Three examiners visually characterized each site independently for signs of demineralization (VI), ditching presence (VD), and color change, and utilized light-induced fluorescence (QLF), and infrared laser fluorescence (LF) techniques. The teeth were sectioned through the selected sites, and the severity of each lesion was determined by confocal laser scanning microscopy (CLSM) as the ‘gold standard’. Agreement among examiners was assessed using weighted kappa statistics and showed fair to moderate correlation with all techniques. Sensitivity, specificity, positive predictive value (PPV), negative predictive value and accuracy were determined by utilizing three arbitrary CLSM thresholds. Higher sensitivity was indicated by the QLF and LF than by VI. For PPV and accuracy, QLF and LF showed values higher or similar to VI. Low sensitivity was found for VD. The results obtained in this study suggest that LF and QLF may improve the ability to detect early secondary caries around amalgam restorations.