The enriched basaltic (martian) shergottite Ksar Ghilane (KG) 002, discovered in 2010, is exceptionally rich in coexisting but discrete apatite and merrillite crystals. It has been selected to better constrain the formation conditions and post-crystallization processes, and thus the evolution of martian rocks based on Ca-phosphates. A petrological, chemical, chronological and microstructural approach using a series of high-spatial resolution techniques including Raman spectroscopy, electron microscopy (SEM, EPMA, CL-imaging) and secondary ion mass spectrometry (SIMS) analysis has been applied to a representative number of Ca-phosphate grains. Analytical results for apatite and merrillite reveal: (i) zoning in F, Cl, Br and I concentrations, (ii) elevated Cl concentrations in the range of ∼11,900–35,300 µg/g and halogen ratios, i.e., Cl/Br and Cl/I, as well as stable chlorine isotope composition, reported as δ37Cl values rel. to Standard Mean Ocean Chloride (SMOC, defined as 0‰) with a value of +0.67 ± 0.14‰ (1σ), distinguishing KG 002 phosphates from that of other enriched and depleted shergottites. The halogen and heavier δ37Cl record indicate a slightly higher degree of ∼3.5% assimilation of Cl-rich and isotopically heavier crustal reservoir on Mars when compared to other enriched shergottites. (iii) Structural investigations together with the chemical and petrological context of the grains confirm the occurrence of hydroxyl-poor merrillite, indicate weak if any alteration effects induced by metamictization, only minor structural modifications due to shock metamorphism, and absence of replacement reactions. Therefore, igneous crystallization of Ca-phosphates from a fractionated, hydrous and ferrous mantle source, rich in volatiles including the halogens and Na and lithophile rare earth-elements, and absence of interaction with crustal fluids/brines of the sample is deduced. (iv) The Pb isotopic composition of six apatite and three merrillite grains is highly unradiogenic and the 238U-206Pb record yields a phosphate crystallization time at 395 ± 240 Ma (2σ), which is similar to those of other enriched shergottites.