Geochemical studies of volcanic rocks in the Gamilaroi terrane and Calliope Volcanic Assemblage, New England Fold Belt, eastern Australia, indicate that the setting in which these rocks formed changed in both space and time. The Upper Silurian to Middle Devonian basalts of the Gamilarol terrane show flat to slightly light rare-earth element (LREE) depleted chondrite normalised patterns, depletion of high field strength elements (HFSE) relative to N-MORB, low TI/V and high Ti/Zr ratios, high NI, Cr and large-ion lithophile element (LILE) contents, features characteristics of intra-oceanic island arc basaltic magmas. They are associated with low-K, less mafic volcanics, showing moderate LREE enrichment, low Nb and Y contents and Rb/Zr ratios. The depletion of HFSE in the basalts indicates that the magmas were derived from a refractory source in a supra-subduction zone setting. The presence of such a zone implies that the arc was associated with a backarc basin, the location of which was to the west where a wide backarc region existed from the Middle Silurian. This polarity of arc and backarc basin suggests that the subduction zone dipped to the west. In contrast to their older counterparts, Middle to Upper Devonian basalts of the Gamilarol terrane have MORB-like chondrite normalised patterns and higher Ti and lower LILE contents. Moreover, they have low Ti/Zr ratios and MORB-like Ti/V ratios and HFSE contents, features typical of backarc basins. Dolerites of the Gamilarol terrane also have predominantly backarc basin signatures. These features suggest that both the basalts and dolerites have been emplaced in an extensional environment produced during the rifting of the intra-oceanic island arc lithosphere. A progressive increase in TI/V ratios, and TiO2 and Fe2O3 contents at constant MgO, of stratigraphically equivalent basalts, towards the north-northwest part of the belt, is consistent with either greater extension to the north or melting of a more fertile magma source. By contrast, basalts in the southeast part of the terrane have moderately high Ti/Zr and low Ti/V ratios and in some samples, exhibit depletion of HFSE, compositional features transitional between island arc and backarc basin basalts. The Lower to Middle Devonian mafic rocks in the Calliope Volcanic Assemblage show both LREE enriched and depleted chondrite normalised REE patterns. Further, the majority have high Ti/Zr ratios and low Zr contents as well as relatively high Th contents relative to MORB. These features are common to rocks of Middle Devonian age as well as those of Early Devonian age and are suggestive of eruption in an arc setting. Thus, the data from this study provide new evidence for the evolution of the New England Fold Belt from the Late Silurian to the Late Devonian and reveal a history more complicated than previously reported.