Since the discovery of electron microscopes, nanomaterials and nanotechnology have been influencing academic and industrial research greatly for bringing out newer and better products with improved materials' properties. In the field of environmental gas sensors too, the demonstration of nanomaterials for sensing various gases has become a common practice. Environmental gas pollution has turned out to be a huge concern in the society due to the progress of civilization. The awareness of health hazard for different toxic/polluting gases and rectification measure by imposing stricter norms has prompted extensive research to develop efficient gas sensors to detect trace level of pollution from various sources. Thin film, ultrathin film, and nanostructure materials of metal oxide semiconductor, polymer, metal, carbon nanotube, graphene, etc. with or without sensitizers have been investigated for sensing various toxic gases. New device structures have been fabricated to achieve high sensitivity, selectivity, fast response, etc. The microstructure and thickness of film are found to influence the performance greatly. Various methods of preparations and mechanism of sensing are being explored. All these aspects and the challenges were discussed in this chapter.