U–Pb ages and Hf isotope compositions of zircons from the Chencai complex in Zhejiang Province have been determined to provide constraints on mechanisms of migmatization and tectonic evolution related to the early Palaeozoic orogeny in the Cathaysia Block, South China. Zircons from leucosome samples of migmatites are characterized by nebulous overgrowths enclosing inherited cores or occur as newly formed grains with weak zoning. Five samples gave weighted mean ages ranging from 438±3 Ma to 432±4 Ma, which are interpreted as recording the time of anatexis of a regional tectono-thermal event. Their εHf(t) values range from −21.4 to −4.8 (with peak at −11), with corresponding TDM2 ages of 1.73–2.77 Ga (with peak at c. 1.9–2.3 Ga), suggesting that the protoliths formed by reworking of ancient crust evolved from Late Palaeoproterozoic – early Archaean crust–mantle differentiation. The migmatization was spatially and temporally associated with reported 460–435 Ma metamorphism with a clockwise pressure–temperature (P–T) path and was most likely controlled by crustal thickening driven by the early Palaeozoic orogenesis. The TDM2 ages of the Chencai complex are consistent with those of the Wuyi–Yunkai structural belt in the Cathaysia Block, but distinct from those (with peak at 2.7–3.0 Ga) of the Badu complex which lacks early Palaeozoic tectono-thermal records. The data support the suggestion that a postulated geological entity, instead of the east domain (the Badu complex being its main part) of the Cathaysia Block, was probably involved in the early Palaeozoic orogeny.