The nepheline syenite pegmatite in the Saima alkaline complex in northeastern China is characterized by REE mineralization, mainly rinkite-(Ce) and associated alteration minerals. As the most abundant REE-bearing mineral in the pegmatite, rinkite-(Ce) closely coexists with microcline, nepheline, natrolite, and calcite. Some rinkite-(Ce) grains show compositional sector-zonation, in which the inner core displays relatively high Ti, Ca, and Sr concentrations, but low Zr, REE, and Na contents. Primary rinkite-(Ce) has undergone multiple episodes of fluid interactions, and accordingly, from weak to strong, three different mineral assemblages of hydrothermal alteration can be summarized: (1) rinkite-(Ce) + secondary natrolite ± K-feldspar ± minor fluorbritholite-(Ce); (2) rinkite-(Ce) relics + secondary natrolite + K-feldspar + fluorbritholite-(Ce) + unidentified Ca-Ti silicate mineral + fluorite and calcite; and (3) pseudomorphs after rinkite-(Ce). The pseudomorphs can be divided into two groups characterized by distinct mineral associations: (1) Ca-bearing strontianite + fluorbritholite-(Ce) + natrolite + fluorite + calcite coexisting with silicate minerals; and (2) calcite + fluorite + fluorbritholite-(Ce) + rinkite-(Ce) relics ± Ca-bearing strontianite ± ancylite-(Ce) associated with a calcite matrix. These alteration mineral assemblages are evidence of magmatic-derived alkali metasomatism due to an alkali-CO2-F-rich fluid and Ca-metasomatism due to a different, externally derived Sr- and Ca-rich fluid. The metasomatic events acted as the potential driving force for the rinkite-(Ce) dissolution and pseudomorph-forming process. The high concentration of rinkite-(Ce) in the nepheline syenite pegmatite results from the fractional crystallization of the Saima CO2-rich alkaline silicate magma, and the successive alterations of rinkite-(Ce) attest to the important role played by hydrothermal fluids in controlling the remobilization of REE and the crystallization of secondary rare earth minerals.