Reductive transformation of nitroaromatic compounds is a central step in its remediation in wastewater, and therefore has invoked extensive catalytical research with rare metals such as palladium (Pd). Herein, we report Pantoea sp. IMH assisted biosynthesis for Pd@NC as an efficient catalyst for the reduction of nitroaromatics. Multiple complementary characterization results for Pd@NC evidenced the evenly dispersed Pd NPs on an N doped carbon support. Pd@NC exhibited the superior catalytic activity in the reduction of nitroaromatic compounds (4-nitrophenol, 2-nitroaniline, 4-nitroaniline, and 2,6-dichloro-4-nitroaniline). The origin of the catalytic activity was explained by its unique electronic structure, as explored with X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory (DFT) calculations. XANES analysis revealed an increase of 25.6% in the d-hole count in Pd@NC compared with Pd, as the result of pd hybridization. In agreement with our experimental observations, DFT calculations suggested the formation of Pd-C bonds and charge re-distribution between Pd and the carbon layer, which contributed to the superior catalytic activity of Pd@NC.