Carotenoids, natural pigments, are a group of chemically heterogeneous molecules, present in numerous taxonomical clusters. Because of their various bioactivities, carotenoids are day-by-day applied in numerous fields. The present work aimed to investigate an efficient extraction process of carotenoids from blue crab shells and their identification by HR-ESI-MS technique. In this context, different methods (enzymatic, maceration, Soxhlet, etc.) and solvents (variable polarity index) were tested. Maceration using the binary system hexane/isopropanol (50/50) was found to be the most efficient process, producing high carotenoids content and low total phenolic and soluble protein amounts (p < 0.05). When combined with an enzymatic pretreatment, this procedure was found to be remarkably (p < 0.05) more efficient and selective especially towards astaxanthin (p < 0.05). The HR-ESI-MS identified 23 compounds, depending on the adopted extraction approach. The compounds identified may have potential for applications in food or pharmaceutical industries.