High thermal conductivity is essential for polymer applications such as electronic chip encapsulation, where efficient heat dissipation ensures system functionality and reliability. Here, we introduce a novel strategy to enhance through-plane thermal conductivity in 2D covalent organic frameworks (COFs). A highly crystalline edge-on 2D polyamide (v2DPA) film achieves a thermal conductivity of 1.16 ± 0.05 W/(mK) at 310 K, surpassing the previous record (1.03 W/(mK) in COF-5 [Evans et al.