Dehydrogenation of formic acid to yield molecular H-2 is a sustainable and promising route in hydrogen energy supply. Rational design of high-performance catalytic system for it remains a challenging task. Herein, CoPd nanoparticles supported on covalent triazine frameworks (CoPd/CTF) were fabricated for the first time. The prepared Co5Pd5/CTF-600 catalyst exhibited 100% H-2 selectivity and excellent catalytic activity (TOF = 2129 h(-1), n(pd)/n(HCOOH) = 0.007) toward the dehydrogenation of formic acid at 50 degrees C. Our study further demonstrated that not only the synergetic effect between CoPd nanoparticles and nitrogen-rich CTF support, but also the ultrafine sizes of CoPd play a key role for the efficient catalytic dehydrogenation from formic acid. This work provides a feasible strategy to design high-performance CTF-based heterogeneous catalyst for catalyzing different reactions.