There is provided a multilayer structure comprising: (i) a heat-resistant outer layer comprising at least one polymer chosen from a polyester, a polypropylene, and mixtures thereof; and (ii) a sealant inner layer comprising at least one metallocene-catalyzed polyethylene, at least one metallocene-catalyzed polyolefin plastomer, or mixtures thereof. The multilayer structure further comprises between the outer an inner layers, in any possible order, a gas barrier layer comprising at least one polyvinylidene chloride polymer, at least one ethylene vinyl alcohol copolymer, or mixtures thereof, and a layer comprising at least one oriented polypropylene polymer. Such a multilayer can be useful for food packaging. There is also provided processes for preparing the multilayer structure.