Thermal bonding into composites of three and more layers is the most suitable method for expanding the applications of electrospun materials. A thermoadhesive based on phenolformaldehyde resins was developed and could be used to duplicate nano- and microfibrous materials while retaining their heat and chemical resistance, structures, and surface properties. The spinning solution composition was optimized in order to prepare the required material structure. The effect of a cross-linking additive on the chemical resistance and adhesive properties of the thermoadhesive was examined. The effect of thermal bonding using this material on the functional properties of electrospun nano- and microfibrous materials was investigated.