Early caries diagnosis still challenges dentistry. Polarization-sensitive optical coherence tomography (PS-OCT) is promising to detect initial lesions non-invasively in depth-resolved cross-sectional visualization. PS-OCT with determined degree of polarization (DOP) imaging provides an intuitive demineralization contrast. The aim of this study is to evaluate the suitability of DOP-based PS-OCT imaging to monitor controlled de- and remineralization progression for the first time and to introduce it as a valid, non-destructive in vitro detection method. Twelve standardized bovine enamel specimens were divided in different groups and demineralized with hydrochloric acid (HCl) as well as partly remineralized with fluoride over a 14-day pH-cycling experiment. The specimens were stored in artificial saliva and sodium chloride (NaCl), respectively. Progress measurements with PS-OCT were made with polarization-sensitive en faceand B-scan mode for qualitative evaluation. The specimens demineralized in HCl showed the most pronounced surface change (lowest DOP) and the most significant increase in depolarization. Additional fluoride treatment and the storage in artificial saliva resulted in the opposite (highest DOP). Therefore, DOP-based PS-OCT imaging appears to be a valuable technique for visualization and monitoring of enamel demineralization and remineralization processes in vitro. However, these findings need to be confirmed in human teeth ex vivo or in situ.