The first high polarization ferroelectric main chain liquid crystalline polymers have been synthesized via hydrosilation polyaddition using α, ω-dihydro(tetramethyldisiloxane) and chiral, low molar mass mesogenic compounds bearing at each end an olefinic group. They exhibit broad, chiral smectic C and smectic A mesophases. Aligned samples have been obtained using a combination of surface and mechanical effects, giving opportunities for fully characterizing the electro-optical properties of the polymers. Very high polarizations have been measured: 600 nC cm−2at room temperature.