We report on the design, fabrication, and performance of a nanoporous, coaxial array capacitive detector for highly sensitive chemical detection. Composed of an array of vertically aligned nanoscale coaxial electrodes constructed with porous dielectric coax annuli around carbon nanotube cores, this sensor is shown to achieve parts per billion level detection sensitivity, at room temperature, to a broad class of organic molecules. The nanoscale, 3D architecture and microscale array pitch of the sensor enable rapid access of target molecules and chip-based multiplexing capabilities, respectively.