Owing to the synergistic compositional and structural advantages, ultrathin bimetallic nanosheet assembly nanostructures are widely recognized as advanced catalysts for alcohol electrooxidation reaction. Although numerous efforts have been made, the fabrication of well-defined ultrathin bimetallic nanosheet assemblies (NSAs) at large scale is still a tough challenge. Herein, a universal synthetic approach has been proposed to produce a series of well-defined Pd-pm (pm = Ga, In, Sn, Pb, Bi) alloy NSAs. Due to multiple merits of their unique 3D flower-like nanostructure and alloyed crystalline features, the self-supported Pd-pm NSAs show excellent electrocatalytic performance for the methanol oxidation reaction (MOR) and glycerol oxidation reaction (GOR). Given the eco-friendly synthetic concept, facile universality, and outstanding electrocatalytic properties of the generated bimetallic Pd-pm NSAs, we believe that this method could be employed for building more advanced nanocatalysts toward efficient electrocatalytic applications.