New restrictions on carbon dioxide emissions and electricity consumption are currently being introduced around the world. Innovative solutions are being adopted in many countries to reduce CO2 emissions and material and energy consumption. The present work is related to the study of innovative binders based on geopolymers for the production of layered building envelopes. The binders are reinforced with composite bars and containing fibers of natural origin. The natural materials used to produce the samples are completely biodegradable. A 10-mol sodium hydroxide solution with an aqueous solution of sodium silicate was used for alkaline activation of geopolymers. The purpose of the study was to compare and determine the insulating properties of natural fiber-based materials such as coconut mat, jute felt, hemp felt, flax felt, flax wool, hemp wool, flax-jute wool, and to determine the effect of these materials on geopolymer composites, in which 4 layers of natural insulating materials were used, and the composites were reinforced by fiberglass bars. The publication presents the results of physicochemical studies of geopolymerization precursors and natural insulating materials, studies of thermal properties of fibers, mats, felts and wools, morphology of fiber structure and texture, as well as physical and thermal properties of finished multi-layer partitions. The results indicate the great potential of these materials in prefabrication and structural-insulation applications. The fabricated composites using 4 layers of natural fibers showed improved thermal conductivity by as much as 40% (reduced thermal conductivity from 1.36 W/m × K to about 0.8 W/m × K). The work may have future applications in energy-saving and low-carbon construction.