Phosphates are a group of complex minerals widespread on Earth that can crystallize in several environments. Changes in environmental conditions during crystallization are reflected in the formation of a sequence of phosphate minerals, termed paragenesis. Accordingly, analyses of textural and chemical properties of complex mineral assemblages are essential to reconstruct the history of rocks and solid materials. Raman mapping can detect those mineralogical changes in complex assemblages with high spatial resolution, successfully determining the paragenetic sequence. Specifically, Raman spectroscopy is more advantageous than conventional methods because it requires little sample preparation, it is nondestructive, and it is capable of identifying hydrated minerals and phases composed of light elements (e.g., H and Li). In this study, the parageneses of two phosphatic assemblages from the Buranga pegmatite, a P–Li–Nb–Ta‐rich magmatic rock, are reported in detail. The first case shows the replacement of primary F‐rich montebrasite [LiAl(PO4)(OH,F)] by secondary F‐poor montebrasite [LiAl(PO4)OH]. Mapping of the OH‐stretching peak position and width identifies the mineral phases, illustrates their spatial relations, and allows to estimate the F content distribution. The second case investigates a sequence of phosphate minerals in a complex assemblage (trolleite + rosemaryite ➔ lazulite–scorzalite ➔ samuelsonite ➔ wardite). The application of multivariate analysis methods to characterize complex assemblages is assessed, and the classical least squares method is identified as the best suited for this setting. An analysis of Raman images shows that Buranga samples experienced a progressive hydration process during cooling, followed by fluid‐assisted mineral reactions with remobilization of elements, such as Ca and Na.