Monolayer and multilayers of ferroelectric liquid crystals (FLC) obtained by the Langmuir-Blodgett (L-B) technique on the water subphase were characterized by surface pressure measurements and by polarization modulated infrared reflection absorption spectroscopy (PM-IRRAS). The specific surface selection rules on the water surface and the high sensitivity of the PM-IRRAS method allow the estimation of the microscopic molecular organization of Langmuir films. Moreover, five layers of FLC were successfully transferred onto CaF2 and gold solid substrates and were studied by conventional Fourier transform infrared spectroscopy and by the PM-IRRAS method. Finally, the influence of the temperature on the structural arrangement of L-B films has been discussed.