Facile production of hydrogen at room temperature is an important process in many areas including alternative energy. In this Communication, a potent boron-doped Pd nanocatalyst (Pd-B/C) is reported for the first time to boost hydrogen generation at room temperature from aqueous formic acid formate solutions at a record high rate. Real-time ATR-IR spectroscopy is applied to shed light on the enhanced catalytic activity of B-doping and reveals that the superior activity of Pd-B/C correlates well with an apparently impeded COad accumulation on its surfaces. This work demonstrates that developing new anti-CO poisoning catalysts coupled with sensitive interfacial analysis is an effective way toward rational design of cost-effective catalysts for better hydrogen energy exploitation.