Changes in mineral content (mainly phosphate) are important for detecting primary dental caries. However, so far, there has not been a device that can provide detailed information on the changes in organic and inorganic content of dental caries during the caries development and sensitively found early dental caries. DIAGNOdent has been widely used as a laser device for detecting dental caries, but it does not provide information about dental inorganics. Our experiment synthesised hydroxyapatite-aromatic amino acids (HA-AAAs), protoporphyrin IX (HA-PPIX), and tetracycline hydrochloride (HA-TCN) complexes as a simple biological mineralization model related to teeth in vitro and achieved single-factor control to avoid impurity interference so that the test results are accurate. For the first time, Raman and DIAGNOdent were used to detect HA-AAAs, HA-PPIX, and HA-TCN and determine the fluorescence characteristics of each organic substance. Our results show that Raman results are consistent with DIAGNOdent readings when detecting complexes and that Raman relative intensity (RRI) calculated by Raman spectroscopy can directly reflect the phosphate content in the sample. This implies that Raman is possible to replace DIAGNOdent as a novel and more accurate caries detector after conversion of the spectrum results. K E Y W O R D S aromatic amino acids, hydroxyapatite, laser-induced fluorescence, protoporphyrin IX, tetracycline hydrochloride 1 | INTRODUCTION Early detection and diagnosis of dental caries, especially "hidden caries," are very important to protect teeth and prolong their service life. Conventional clinical methods such as visual inspection, probing, magnifying glasses, and bitewing radiography result in low sensitivity values for detecting occlusal caries. [1-5] The lowest sensitivities are found in teeth exhibiting macroscopically whole occlusal surfaces but with potential dentinal caries histologically called "hidden caries," which are found in 10-50% of teeth with dentinal caries. [1-5] A device named DIAGNOdent (DD) has been introduced based on the theory of irradiating teeth with red light for excitation at 655 nm. Carious spots exhibit a stronger fluorescence signal than sound teeth, and there is higher background Kainan Zhang and Xinjie Cai contributed equally to this article.