Avalonia, the largest accreted crustal block in the Appalachian orogen, consists of Neoproterozoic magmatic arc sequences that represent protracted and episodic subduction-related magmatism before deposition of an Ediacaran–Ordovician cover sequence including siliciclastic rocks. Zircon crystals were obtained from arc-related magmatic rocks and from clastic sedimentary sequences and analyzed in situ for their Hf-isotope composition. The majority of magmatic and detrital zircons are dominated by initial 176Hf/177Hf values that are more radiogenic than chondritic uniform reservoir (CHUR) with calculated crust formation Hf–TDM model ages that range from 0.84 to 1.30 Ga. These results suggest formation by partial melting of juvenile mantle in a Neoproterozoic continental arc. Some zircons have Hf–TDM model ages ca. 1.39–3.09 Ga with εHf values of –33.9 to –0.5 and more clearly indicate involvement of older lithosphere in their petrogenesis. Whole-rock Sm–Nd isotopic compositions from felsic volcanic rocks are characterized by positive initial εNd values with Mesoproterozoic depleted mantle model ages consistent with juvenile extraction. Results suggest a dominant mantle component with long-term light rare earth element (LREE) depletion mixed with an older crustal component with long-term LREE enrichment. The pattern of TDM model ages and variations in Lu–Hf and Sm–Nd isotopic character are compatible with a ca. 1.0–1.2 Ga igneous tectonomagmatic event that formed basement to Neoproterozoic magmatic arcs in Avalonia. The presence of evolved isotopic signatures, however, indicates that significant older Proterozoic crust is present locally beneath Avalonia, suggesting that Avalonia formed in a single Neoproterozoic arc system that generated juvenile mantle-derived crust, coupled with lesser anatectic reworking of significantly older crust.