Long-chain alkyl silicone is a type of modified silicones that finds potential applications in various areas. Long-chain alkyl fluorosilicone (LCAFS) can be considered as a modified long-chain alkyl silicone as it synergistically combines the properties of long-chain alkyl silicone and novel fluorosilicone. As far as we know, reports on the synthesis of LCAFS are rare. In this report, a facile method to synthesize LCAFS was explored. It was found that silicone bearing novel C30-45 alkyls and trifluoropropyl pendent groups, namely (C30-45 alkyl) methylsiloxane/trifluoropropylmethylsiloxane copolymer (TF-AMS), could be synthesized via a simple siloxane equilibration process between silanol-terminated polytrifluoropropylmethylsiloxane and (C30-45 alkyl)methyl silicone, a commercially available silicone that is generally considered as unreactive. The chemical structure of TF-AMS was characterized unambiguously by FTIR, NMR, GPC and DSC. The thermal stabilities of TF-AMS were investigated by TGA. Based on our experimental results, a plausible mechanism for the synthesis of TF-AMS was proposed. Graphic abstract A novel long-chain alkyl fluorosilicone was synthesized via a simple yet efficient siloxane equilibration process. [GRAPHICS] .