A simple solvothermal method was developed to prepare N-doped reduced graphene oxide supported homogeneous PtCo nanodendrites (PtCo NDs/N-rGO), where ethylene glycol (EG) served as the reducing agent and the solvent, and linagliptin as the structure-directing and stabilizing agent for PtCo NDs and dopant for rGO, respectively. Controlled researches showed that the dosage of linagliptin and the ratios of the two metal precursors were important in the current synthesis. The PtCo NDs/N-rGO nanocomposite exhibited higher catalytic activity towards the reduction of 4-nitrophnol (4-NP) in contrast with the referenced Pt1Co3 NCs/N-rGO, Pt3Co1 NCs/N-rGO and commercial Pt/C catalysts. More importantly, the constructed catalyst exhibited the superior stability without sacrificing the catalytic activity, showing great prospect for the reduction of 4-NP in practice.