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The building sector, one of the most energy-consuming, is among the most current topics due to the maturing concerns about the anthropogenic factor’s impact on CO₂ quantities in the atmosphere and its association with global temperature rise. Using sustainable building materials is a promising alternative in building envelope applications to improve in-use energy efficiency. These materials, having a low environmental impact, the advantage of being renewable, and low embodied energy, contribute to global sustainability. This comprehensive literature review presents a broad overview of these materials’ hygrothermal characteristics, thermal performance, and energy use. The main goal is to compile the most important research findings on these materials’ capabilities for building construction and their contributions and effects on energy performance and thermal insulation.