The Harihada–Chegendalai ophiolitic mélange, which is located between the Bainaimiao arc and the North China Craton, holds significant clues regarding the tectonic setting of the southern margin of the Central Asian Orogenic Belt. The ophiolitic mélange is mainly composed of gabbroic and serpentinized ultramafic rocks. Here, zircon U–Pb dating, in situ zircon Hf isotopic, whole-rock geochemical and in situ mineral chemical data from the ophiolitic mélange are reported. The zircons in the gabbroic rocks yielded concordia U–Pb ages of 450–448 Ma and exhibited slightly positive ϵHf(t) values (0.87–4.34). The geochemical characteristics of the gabbroic rocks indicate that they were generated from a mantle wedge metasomatized by subduction-derived melts from sediments with continental crust contamination, in a fore-arc tectonic setting. These rocks also experienced the accumulation of plagioclase. The geochemical characteristics of the ultramafic rocks and their Cr-spinels indicate that they may constitute part of residual mantle that has experienced a high degree of partial melting and has interacted with fluids/melts released from the subducted slab in the same fore-arc tectonic setting. The ophiolitic mélange may therefore have formed in this fore-arc tectonic setting, resulting from the northward subduction of the South Bainaimiao Ocean beneath the Bainaimiao arc during Late Ordovician time, prior to the collision between the Bainaimiao arc and the North China Craton during the Silurian to Carboniferous periods.