Metamorphosed basalts, basaltic andesites, andesites and plagiorhyolites of the Early Cretaceous, probably pre-Albian, Maimón Formation, located in the Cordillera Central of the Dominican Republic, are some of the earliest products of the Greater Antilles arc magmatism. In this article, new whole-rock element and Nd-Pb radiogenic isotope data are used to give new insights into the petrogenesis of the Maimón meta-volcanic rocks and constrain the early evolution of the Greater Antilles paleo-arc system. Three different groups of mafic volcanic rocks are recognized on the basis of their immobile element contents. Group 1 comprises basalts with compositions similar to low-Ti island arc tholeiites (IAT), which are depleted in light rare earth elements (LREE) and resemble the forearc basalts (FAB) and transitional FAB-boninitic basalts of the Izu-Bonin-Mariana forearc. Group 2 rocks have boninite-like compositions relatively rich in Cr and poor in TiO2. Group 3 comprises low-Ti island arc tholeiitic basalts with near-flat chondrite-normalized REE patterns. Plagiorhyolites and rare andesites present near-flat to subtly LREE-depleted chondrite normalized patterns typical of tholeiitic affinity. Nd and Pb isotopic ratios of plagiorhyolites, which are similar to those of Groups 1 and 3 basalts, support that these felsic lavas formed by anatexis of the arc lower crust. Geochemical modelling points that the parental basic magmas of the Maimón meta-volcanic rocks formed by hydrous melting of a heterogeneous spinel-facies mantle source, similar to depleted MORB mantle (DMM) or depleted DMM (D-DMM), fluxed by fluids from subducted oceanic crust and Atlantic Cretaceous pelagic sediments. Variations of subduction-sensitive element concentrations and ratios from Group 1 to the younger rocks of Groups 2 and 3 generally match the geochemical progression from FAB-like to boninite and IAT lavas described in subduction-initiation ophiolites. Group 1 basalts likely formed at magmatic stages transitional between FAB and first-island arc magmatism, whereas Group 2 boninitic lavas resulted from focused flux melting and higher degrees of melt extraction in a more mature stage of subduction. Group 3 basalts probably represent magmatism taking place immediately before the establishment of a steady-state subduction regime. The relatively high extents of flux melting and slab input recorded in the Maimón lavas support a scenario of hot subduction beneath the nascent Greater Antilles paleo-arc. Paleotectonic reconstructions and the markedly depleted, though heterogeneous character of the mantle source, indicate the rise of shallow asthenosphere which had sourced mid-ocean ridge basalts (MORB) and/or back-arc basin basalts (BABB) in the proto-Caribbean domain prior to the inception of SW-dipping subduction. Relative to the neighbouring Aptian-Albian Los Ranchos Formation, we suggest that Maimón volcanic rocks extruded more proximal to the vertical projection of the subducting proto-Caribbean spreading ridge.