A layered, covalent, triazine-based framework (CTF) was synthesized via the condensation of 2,6-naphthalenedicarbonitrile under ionothermal conditions. The polytrimerization of this bi functional carbon nitrile in zinc chloride at lower temperatures yields a well-ordered, close-packed framework. At elevated temperatures an amorphous, yet porous solid is obtained, which shows remarkable thermal stability (640 °C) and a high surface area (2255 m2 g−1 and 1.51 cm3 g−1). Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.