Phospholipids are widely used as mimetic systems to exploit interactions involving biological membranes and pharmacological drugs. In this work, the layer-by-layer (LbL) technique was used as a new approach to produce multilayered thin films containing biological phospholipids applied as transducers onto Pt interdigitated electrodes forming sensing units of an electronic tongue system. Low concentrations (nM level) of a phenothiazine compound were detected through impedance spectroscopy. Both negative 1,2-dipalmitoyl-sn-3-glycero-[phosphor-rac-(1-glycerol)] (DPPG) and zwitterionic l-alpha-1,2-dipalmitoyl-sn-3-glycero-phosphatidylcholine (DPPC) phospholipids were used to produce the LbL films, whose molecular architecture was monitored combining spectroscopy and microscopy at micro and nanoscales. The sensor array was complemented by Langmuir-Blodgett (LB) monolayers of DPPG and DPPC deposited onto Pt interdigitated electrodes as well. It was found that the distinct molecular architecture presented by both LbL and LB films plays a key role on the sensitivity of the sensor array with the importance of the LbL films being demonstrated by principal component analysis (PCA).