The hard-segment phase thermal transitions and heat-resistance of benzidine-modified-montmorillonite (BZD-Mont)/polyurethane nanocomposites of different hard segment contents were found to be affected by a small amount of BZD-Mont. In particular, the presence of less than 5 wt% layered silicates from BZD-Mont can result in hard segments not only having a more thermally stable long-range order and a higher melting temperature, but also showing a loss of crystallinity of the hard segment in polyurethane. Additionally, the degradation temperature of BZD-Mont/polyurethane nanocomposite was slightly higher than that of pure polyurethane.