Room temperature HCHO catalytic oxidation over inert support loaded Pd catalysts remains a significant challenge. Herein, a series of alkali Na (1–4 wt.%) modified 1Pd/SBA‐15 catalysts were prepared by a co‐impregnation method and used for HCHO catalytic oxidation at room temperature. Results showed that alkali Na significantly improved the HCHO oxidation performance of 1Pd/SBA‐15 and the optimal Na loading was 2 wt.%. BET, XRD, STEM, XPS, H2‐TPR, O2‐TPD and in situ DRIFTS were performed to reveal the promotion role of alkali Na. As a consequence, alkali Na addition could stabilize well dispersed Pd particles which then facilitated the O2 activation and accelerated the decomposition of formate intermediates species, thus a superior HCHO catalytic oxidation performance was obtained. This study first clearly illustrated the promotion mechanism of alkali Na without the implication of active support and provides an efficient and facile way to achieve high dispersion of Pd particles on inert support and tremendously expands the selected range of supports for room temperature HCHO catalytic oxidation.