A review article aiming to present the actual state of the art on the development and the assessment of cool materials (i.e. materials with high solar reflectance and infrared emittance) for buildings and urban structures. The research in this field is roughly divided in four phases and includes the development and assessment of: (a) highly reflective and emissive light colored materials, (b) cool colored materials, i.e. colored materials with increased near infrared and thus overall solar reflectance compared to similarly colored conventional ones, (c) phase change materials and (d) dynamic cool materials. All major aspects related to each technology are described and the benefits and impacts of these materials at building, city and global scale are reported. The wide use of such materials can significantly contribute to the mitigation of the heat island effect and the improvement of urban environmental quality.