Background: In prosthodontics, achieving esthetic success requires precise shade matching of restorations to natural teeth. This study evaluated the shade-matching abilities of fourth-year dental students using different tools and conditions in laboratory (LB) and clinical (CL) settings. Methods: In the LB setting, students matched blinded shade tabs to the VITA classical shade guide under natural daylight (ND), artificial light (AL), and a polarized filter (PF). In the CL setting, they determined the shades of patients’ central incisors using the same conditions. Participants also completed a questionnaire about their experience. Results: Quantitative analysis showed better shade matching in the LB setting, particularly with the PF (52% correct), compared to ND (50%) and AL (43%). In the CL setting, overall accuracy dropped to 32% across all conditions. No results were statistically significant. Qualitative feedback revealed that students found the spectrophotometer to have improved their accuracy and reliability compared to the ND and AL conditions. Conclusions: This study highlights the importance of incorporating technology as a validation tool in dental practice. Leveraging tools like spectrophotometers may enhance shade-matching accuracy, streamline processes, and improve patient satisfaction while balancing traditional methods with technological advancements.