A rapidly self-healable polymer is highly desirable but challenging to achieve. Herein, we developed an elastomeric film with instant self-healing ability within 10 s at room temperature. For this purpose, a series of copolymers of poly(glycidyl methacrylate-co-2-hydroxyethyl acrylate) (poly(GMA-co-HEA), or pGH) were synthesized in the vapor phase via an initiated chemical vapor deposition (iCVD) process. The elastomer includes a large amount of hydroxyl groups in the 2-hydroxyethyl acrylate (HEA) moiety capable of forming rapid, reversible hydrogen bonding at room temperature, while glycidyl methacrylate (GMA) with a rigid methacrylic backbone chain in the copolymer provides mechanical robustness to the elastic copolymer. With the optimized copolymer composition, pGH indeed showed instant recovery of the toughness within a minute; a completely divided specimen could be welded within a minute at room temperature and under ambient conditions simply by placing the pieces in close contact, which showed the outstanding recovery performance of elastic modulus (93.2%) and toughness (15.6 MJ m-3). The rapid toughness recovery without supplementing any external energy or reagents (e.g. light, temperature, or catalyst) at room temperature and under ambient conditions will be useful in future wearable electronics and soft robotics applications.