Ultramafic rocks and high-Cr chromite ore from the Almaz-Zhemchuzhina deposit, the largest in the Main ore field of the Kempirsai massif, have been studied. The detailed mineralogical and geochemical examination of deep structure test and exploratory boreholes allowed us to establish the rough stratification of ultramafic rocks and to demonstrate the position of unique chromite deposits in the generalized vertical section of the southeastern Kempirsai massif. From top to bottom, a barren harzburgite-lherzolite series gives way to an ore-bearing dunite-harzburgite complex with the largest chromite deposits, including the unique Almaz-Zhemchuzhina deposit, in its upper portion and then to pyroxene-free dunite densely impregnated with chromite in the upper part and containing sparsely disseminated chromite at its base. The lower unit is composed of a barren lherzolite-harzburgite series transformed into blastomylonites near the contact with dunite, suggesting a tectonically doubled section in the southeastern part of the massif. The synore asymmetric geochemical zoning developed in the course of formation of chromite deposits as a result of removal of oreforming iron-group elements from the underlying and wall ultramafic rocks into the overlying rocks. Host rocks with disturbed initial proportions of Cr, Fe, Ni, and Mn, together with orebodies, made up ore-bearing zones no less than 1 km in thickness and subdivided into supra-, inter-, and subore subzones. The subore and wall rocks are characterized by partial loss (wt %) of Cr2O3(0.1), NiO (0.04), FeOtot(0.5), and MnO (0.02) and their removal into the interore and supraore (0.03 NiO) subzones. Thus, the subore ultramafic rocks served as a source of ore-forming components, while the interore zone with orebodies occurring therein served as a zone of discharge of these components. Using Mossbauer spectroscopy, the crystal chemistry of iron ions was studied in a representative selection of Cr-spinel samples from rocks and ores of the southeastern and western blocks (the Almaz-Zhemchuzhina and Geophysical XII deposits). The degree of iron oxidation in the samples varies from 8 to 33%. In most cases, a difference in degree of iron oxidation is established in stoichiometric approximation and from Mossbauer data. In other words, the integral stoichiometry of ferrous and ferric ions is disturbed. Such a disturbance may be related not only to partial inversion of the Cr-spinel structure but also to local heterogeneity of the mineral at the micro- and nanolevels with clustering of cations and formation of their associates. An empirical correction of the olivine-Cr-spinel geothermometer and oxybarometer has been performed. The inverse correlation between oxygen fugacity and degree of depletion of ultramafic rocks indicates that these rocks were formed in a closed system with participation of a water-methane fluid. Along with stratification of ultramafics, this correlation testifies to a powerful asthenospheric source of reduced fluids. The retention of low oxygen fugacity in central portions of orebodies does not rule out that after a break this source participated in the formation of unique chromite deposits in the Kempirsai massif.