A facile and robust strategy has been developed to synthesize Pt, Pd, Au, Ag, Pt–Pd, Pd–Ru, Pd–Au, Pd–Cd, and Pt–Cu three-dimensional porous network-like nanostructures (3DPNN) by the synergism of interparticle electrostatic repulsion modulation and heat-induced fusion during nucleation and growth. The size and composition of 3DPNN can be adjusted by varying the amount and the molar ratio of metal precursors. Thus, noble metals and alloy 3DPNN are expected to find promising applications in electro-catalysis, separation, sensors and fuel cells. Furthermore, the simple thermodynamic controlling method might be extended to fabricate other network-like metals and metal oxides with improved physical and/or chemical properties.