The synthesis of fluorinated hybrid silicones prepared in three steps from H2C = CH-C6F12-CH = CH2 (I) and H2C = CHCH2-C6F12-CH2CH = CH2 (II) is presented. First, both hydrosilylations of chlorodimethylsilane with these nonconjugated dienes were carried out in the presence of the Speier’s catalyst leading to the expected bis-chlorosilane in excellent yield from (II) but giving a rearranged by-product from (I). However, a similar reaction from (I) initiated by a peroxide produced the expected bis-chlorosilane selectively. Second, these chlorosilanes were quantitatively hydrolyzed into the corresponding alpha,omega-bis silanols, whatever the spacer between the fluorinated group and the silicon atom. Finally, the polycondensations of these bis silanols were performed in the presence of an amine/acid adduct catalyst. Interestingly, the dihydroxysilane produced from (I) reacts much quicker than the other one. Moreover, thermal properties (T-g, T-dec) were investigated and compared to those of commercially available fluorosilicones or mentioned in the literature and show improvement of the behavior of these fluorosilicones at low and high temperatures.