We present the preparation and characteristics of liquid-phase sensors based on nano-porous silicon multilayer structures for determination of organic content in gasoline. The principle of the sensor is a determination of the cavity-resonant wavelength shift caused by refractive index change of the nano-porous silicon multilayer cavity due to the interaction with liquids. We use the transfer matrix method (TMM) for the design and prediction of characteristics of microcavity sensors based on nano-porous silicon multilayer structures. The preparation process of the nano-porous silicon microcavity is based on electrochemical etching of single-crystal silicon substrates, which can exactly control the porosity and thickness of the porous silicon layers. The basic characteristics of sensors obtained by experimental measurements of the different liquids with known refractive indices are in good agreement with simulation calculations. The reversibility of liquid-phase sensors is confirmed by fast complete evaporation of organic solvents using a low vacuum pump. The nano-porous silicon microcavity sensors can be used to determine different kinds of organic fuel mixtures such as bio-fuel (E5), A92 added ethanol and methanol of different concentrations up to 15%.