The catalytic properties of the Au/C catalyst toward glycerol electrooxidation in alkaline medium have been tremendously improved by an incorporation of Au with Ag. In this work, the catalytic performance of the AuAg/C was further improved by introducing small amount of a third metal, Pd. The catalysts were synthesized by a facile synthesis using the co-reduction of metal precursors in the presence of polyvinyl alcohol. Two series of catalysts with Au:Ag atomic ratios of 1:4 and 1:8 were prepared. Each series consisted of 4 catalysts with various ratios of Au:Pd ranging from 1:0.1 to 1:0.2 and a catalyst without Pd. The resulting metal nanoparticles were formed as nanonetworks with Ag-rich shell. The catalytic activity of the Pd-promoted AuAg-based catalysts was superior over the unpromoted one except for the AuAgxPd0.2/C in which containing too high Pd amount. The most active catalyst was AuAg4Pd0.1/C yielding 2.5 times higher current density than did the AuAg4/C catalyst. Hence, the proposed catalyst model makes use of the surface modifications of the segregated surface, which may influence further catalyst designs for other applications.