Three special types of xenoliths have recently been found in an aegirine–augite syenite porphyry in Liuhe, Yunnan, China. Petrographical, petrochemical, electron microprobe, and scanning electron microscopy studies indicate that pure calcite xenocrysts and quartz-bearing topaz pegmatite xenoliths result from the degassing of mantle fluids during their migration, and that black microcrystalline iron-rich silicate-melt xenoliths are the product of the extraction of mantle fluids accompanying degassing and are composed dominantly of quartz, chlorite, and iron-rich columnar and sheet silicate minerals with characteristic minerals, such as native iron, apatite, and zircon. According to the bulk-rock chemical and mineral compositions and crystallization states, the microcrystalline melt xenoliths are not the product of conventional magmatism, and especially the existence of native iron further proves that the xenoliths were mantle fluid materials under reduction or anoxic conditions. The study of the special xenoliths furnishes an important deep-process geochemical background of polymetallic mineralization in different rocks and strata in the study area.