The computer screen photo assisted technique (CSPT) has been used to develop a hyphenated optical-potentiometric sensing at-ray, based on porphyrinoid materials dispersed into PVC membranes. Sensing layers have been deposited onto indium tin oxide (ITO) glass slides, which were exploited as electrodes, for potentiometric measurements, and chromophore spots, to obtain CSPT data. Both measurements were contemporaneously carried out in the hyphenated sensing platform. The performances of the hyphenated sensing array were first tested for the detection of model analytes, characteristics of vegetable oil matrices, and then evaluated in the discrimination of real samples of olive and seed oils. The results obtained demonstrated that the hyphenated system affords a significant improvement of information and oils classification with respect to the individual potentiometric and optical components.