A novel microfabrication technique for microelectrode arrays (MEAs) with a full diamond–cell interface is demonstrated. Boron-doped nano-crystalline diamond (BNCD) is used as a conductive electrode material on metal tracks insulated by intrinsic NCD. MEAs successfully recorded spontaneous electrical activity in rat primary cortical neuronal cultures. Patch-clamp measurements show no alterations to cell membrane passive properties or active firing response, for cell developing ex vivo on diamond. Impedance analysis revealed low impedance magnitude of BNCD electrodes, suitable for multi-unit neuronal recordings. Additionally, the impedance phase of the fabricated electrodes shows a high degree of capacitive coupling, ideal for neuron stimulation.