P(N‐phenylmaleimide‐alt‐styrene) (PNS) was synthesized, and nylon 6 (PA6)/PNS blends were prepared by melt blending. The heat resistant and crystallographic properties of PA6/PNS blends with different contents were investigated and analyzed. The results showed that the heat deflection temperature (HDT), relative crystallinity (Xn), and dynamic viscosity (η) increased with increasing PNS. The results of differential scanning calorimetry proved that PNS had played a positive role in nucleating PA6. Scanning electron microscosopy showed that the PNS domains were between 0.2 and 4 μm in diameter. The experimental results indicated that the addition of PNS improved the rigidity of PA6/PNS blends, thereby improving the heat‐resistant properties of these blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47689.