Neuronal communication relies on cooperation between the chemical and electrical patterns of neurons. Thus, techniques for illustrating the linkage of the neurochemical events and action potentials with high temporal and spatial resolution is imperative to gain a comprehensive understanding of the intricacies of brain function. Herein, we integrate galvanic redox potentiometry (GRP) and electrophysiological recording onto a 16-site Au microelectrode array (MEA), one of which is for indicating the ascorbate concentration while the others for single-unit activity assessment. The electrochemical probing site was modified with single-walled carbon nanotubes to promote electron-transfer kinetics of ascorbate at low overpotential so as to enlarge the driving force for the spontaneous ascorbate/O2 cell reaction. The resulting GRP-based MEA outputs open-circuit potential that is in a linear relationship with the logarithmic ascorbate concentration and exhibits high selectivity against a set of coexisting electroactive species. Furthermore, no reciprocal interference between the two recording systems is observed during concurrent GRP sensing of ascorbate and single-unit recording in a rat brain. In vivo feasibility of the GRP-based MEA is demonstrated by synchronous real-time measurement of ascorbate release and electrical activity from multiple neuronal populations during spreading depression. Our GRP-based MEA sensor creates new opportunities to realize high-throughput screening or mapping of neurochemical patterns in a larger dimension and correlate them to neuron functions across a spatial scale.