Chemical synaptic transmission between neurons is believed to take place at specialized sites of cell contact, comprising presynaptic terminals and postsynaptic membranes. Neurotransmitter release has been shown to occur also extrasynaptically, mainly targeting glial cells. In a recent study, we investigated the mechanism of extrasynaptic glutamate and ATP release along sensory axons in the olfactory nerve layer. Transmitter release was mediated by calcium-dependent vesicle fusion and triggered calcium transients in adjacent glial cells. These calcium transients were coupled to vasoresponses, indicating that glial calcium signaling mediates neurovascular coupling not only in synaptic brain regions such as gray matter, but also in brain regions devoid of synapses.