The combination of hydrophobic polydimethylsiloxane (PDMS) blocks with hydrophilic polyether segments plays a key role for silicone surfactants. Capitalizing on the double metal cyanide (DMC) catalyst, the direct (i.e., statistical) copolymerization of cyclic siloxanes and epoxides is shown to be feasible. The solvent‐free one‐pot copolymerization of hexamethylcyclotrisiloxane and propylene oxide results in the formation of gradient propylene oxide (PPO)‐PDMS copolymers. Copolymers with up to 46% siloxane content with low dispersities (Ð < 1.2) are obtained in the molecular weight range of 2100–2900 g mol–1. The polymerization kinetics are investigated by pressure monitoring and in situ 1H and in situ 29Si NMR spectroscopy. Contact angle measurements reveal the impact of siloxane incorporation manifest in strongly increased hydrophobicity of PPO‐PDMS copolymers and a glass transition of −95 °C for 46% SiO content. This unusual copolymerization offers promise for the synthesis of silicone/polyether polyols.