Insulating layers based on oxides and nitrides provide high capacitance, low leakage, high breakdown field and resistance to electrical stresses when used in electronic devices based on rigid substrates. However, their typically high process temperatures and brittleness make it difficult to achieve similar performance in flexible or organic electronics. Here, we show that poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane) (pV3D3) prepared via a one-step, solvent-free technique called initiated chemical vapour deposition (iCVD) is a versatile polymeric insulating layer that meets a wide range of requirements for next-generation electronic devices. Highly uniform and pure ultrathin films of pV3D3 with excellent insulating properties, a large energy gap (>8 eV), tunnelling-limited leakage characteristics and resistance to a tensile strain of up to 4% are demonstrated. The low process temperature, surface-growth character, and solvent-free nature of the iCVD process enable pV3D3 to be grown conformally on plastic substrates to yield flexible field-effect transistors as well as on a variety of channel layers, including organics, oxides, and graphene.