Trilobites from mudstone of the Upper Ordovician Xiazhen Formation of South China are described. The reef-associated, unique fauna comprises 25 species, 14 genera, and ten families. Five new species are named: Remopleurides xiazhenensis sp. nov., Hibbertia aodiensis sp. nov., Vietnamia yushanensis sp. nov., Ceraurinus zhuzhaiensis sp. nov., and Pliomerina tashanensis sp. nov. The paucity of trilobites in reef-associated carbonates is interpreted that the trilobites diversified after the reef system decimated. Compared to the Late Ordovician trilobite faunas in other areas of South China, the Xiazhen mudstone fauna is unique in that the phacopids including Vietnamia, Ceraurinus, and Pliomerina account for 75% of the specimens collected. The occurrence of the same trilobite assemblage at different sampling localities along the dip direction of the formation suggests that the outcrops may be overlapped due to structural movement. The Xiazhen trilobite fauna is unique among the Late Ordovician fauna in that it is predominated by phacopids and associated with reef.