Closed-cell foams are widely applied as insulation and essential for the thermal management of protective garments for extreme environments. In this work, we develop and demonstrate a strategy for drastically reducing the thermal conductivity of a flexible, closed-cell polychloroprene foam to 0.031 ± 0.002 W m−1 K−1, approaching values of an air gap (0.027 W m−1 K−1) for an extended period of time (>10 hours), within a material capable of textile processing. Ultra-insulating neoprene materials are synthesized using high-pressure processing at 243 kPa in a high-molecular-weight gas environment, such as Ar, Kr, or Xe. A Fickian diffusion model describes both the mass infusion and thermal conductivity reduction of the foam as a function of processing time, predicting a 24–72 hour required exposure time for full charging of a 6 mm thick 5 cm diameter neoprene sample. These results enable waterproof textile insulation that approximates a wearable air gap. We demonstrate a wetsuit made of ultra-low thermally conductive neoprene capable of potentially extending dive times to 2–3 hours in water below 10 °C, compared with <1 hour for the state-of-the-art. This work introduces the prospect of effectively wearing a flexible air gap for thermal protection in harsh environments.