To precisely discuss the influence of secondary metals on the whole nanosystem, two different types of Pd/Au dimers are constructed by reducing Au precursors with or without ascorbic acid. The number and size of gold nanoparticles attaching on larger Pd nanocrystals can be roughly controlled. Furthermore, based on electrocatalysis, we find that multidecorated dimers are generally more active than singly decorated ones. Meanwhile, the amount of Au precursor used in preparing multidecorated dimers is found to be very important to the catalytic activity of the as-prepared catalysts. The performance of the catalyst is enhanced with the increasing of Au precursor when the Au/Pd molar ratio is below 1:4, but hindered when the ratio climbs higher. Finally, this work provides a promising approach in forming hybrid nanocompositions to find an optimized amount of secondary metal, which is of significance in academic and economic fields.