A promising approach to enhance catalytic performance of supported heterogeneous nano-metal catalysts is to uniformly disperse active nanoparticles on the support. In this work, N-doped carbon-modified graphene (G@NC) nanosheet is designed and prepared to anchor Pd–Fe bimetallic nanoparticles (Pd–Fe/G@NC). The N-doped carbon modification on graphene surface could construct a sandwich-like structure (G@NC), which not only prevented the re-stacking of graphene nanosheets but also provided confined space for stable anchoring of bimetallic Pd–Fe nanoparticles. Benefitted from the unique structural property and synergetic effect of metal Pd and Fe species, the as-obtained Pd–Fe/G@NC composite displays excellent catalytic activity toward 4-nitrophenol reduction reaction with a turnover frequency of 613.2 min− 1, which is far superior to that of the mono-metal counterparts (Fe/G@NC and Pd/G@NC). More importantly, Pd–Fe/G@NC catalyst also exhibits favorable catalytic performance in the reduction of other nitroaromatic compounds (nitrobenzene, 4-nitrotoluene, 4-chloronitrobenzene, and so on). In addition, Pd–Fe/G@NC can catalyze the oxidation of furfuraldehyde to furoic acid with a high yield of 88.64%. This work provides a new guide for rationally designing and developing advanced supported heterogeneous bimetallic catalyst.