This review aims to provide a comprehensive overview of nano- and microscopic materials that can provide thermal radiation insulation without reducing visible light transmittance, thereby reducing heat loss and conserving energy in greenhouses. We also reviewed the radial and thermal properties of greenhouse covering materials. Fillers, colorants, reinforcers, and additives, as well as glass, plastic film, and plastic sheet materials, were discussed. Additionally, by searching for keywords like insulation film, insulation agent, and infrared insulation, compounds based on graphene and fullerene as well as phase transition materials (PCMs) that may be used for radiation insulation, we proposed their potential use in greenhouse covers. They can be divided into semi-transparent photovoltaic (PV) materials, zinc oxide-based film fillers, and silica filter films. We discussed the radiation heat insulation and light transmission characteristics of these materials. Nano-synthesis techniques were also investigated. Based on latest advances in the literature, future developments in the micro- and macroscale synthesis of nanomaterials will enable additional innovations in covering materials for greenhouse structures. A limiting factor, though, was the high sensitivity of PVs to external climatic and meteorological variables. The ability of materials used to make greenhouse covers to control the microclimate, reduce CO2 emissions, use less energy, and increase agricultural productivity, however, cannot be disputed. Similar to this, a thorough examination of the uses of various greenhouse technologies reveals that the advancements also have financial advantages, particularly in terms of reducing greenhouse heating and cooling expenses. The PCMs, which decreased greenhouse-operating costs by maintaining constant ambient temperatures, provide ample evidence of this.