In this work, we have enhanced the capability of an e-nose system based on combined optical and electrochemical transduction within a single gas sensor array. The optical part of this e-nose is based on detection of the absorption changes of light emitted from eight light emitting diodes (LEDs) as measured by a CMOS photo-detector. The electrochemical part works by measuring the change in electrical resistivity of the sensing materials upon contact with the sample vapor. Zinc-5,10,15,20-tetra-phenyl-21H,23H-porphyrin (ZnTPP) and multi-walled carbon nanotube (MWCNT) composite was used as the sensing materials based on its good optoelectronic properties. This sensing layer was characterized by UV-Vis spectroscopy and atomic force microscope and tested with various VOC vapors. Density functional theory (DFT) calculations were performed to investigate the electronic properties and interaction energies between ZnTPP and analyte molecules. It can be clearly seen that this hybrid optical-electrochemical electronic nose system can classify the vapor of different volatile organic compounds.