The development of an efficient synthesis method to produce multimetallic nanoparticles (NPs) with a desirable structure is strongly required to clarify the structure-composition-property relationship of NPs and to investigate their possible applications. However, the controlled synthesis of NPs consisting of multiple (n >= 3) noble metal components has been relatively unexplored in comparison to bimetallic NPs. In the present work, we have demonstrated a facile one-pot aqueous approach for the controlled synthesis of trimetallic Au@PdPt core-shell NPs with a well-defined octahedral Au core and a highly crystalline dendritic Pd-Pt alloy shell (Au-oct@PdPt NPs). The simultaneous reduction of multiple metal precursors with dual reducing agents, namely, ascorbic acid and hydrazine, gave a fine control over the nucleation and growth kinetics of NPs, resulting in the formation of novel Au-oct@PdPt NPs. The prepared NPs showed excellent catalytic performance for methanol electrooxidation, which can be attributed to their optimized binding strength toward adsorbate molecules due to the improved charge transfer between core and shell of the NPs. The present strategy can offer a convenient and valuable way to fabricate multicomponent nanostructures with desired structures and functions.