The morphology of three-dimensional (3D) cross-linked electrodeposits of copper and tin was investigated as a function of the content of metal sulfate and acetic acid in a deposition bath. The composition of copper sulfate had little effect on the overall copper network structure, whereas that of tin sulfate produced significant differences in the tin network structure. The effect of the metal sulfate content on the copper and tin network is discussed in terms of whether or not hydrogen evolution occurs on electrodeposits. In addition, the hydrophobic additive, i.e., acetic acid, which suppresses the coalescence of evolved hydrogen bubbles and thereby makes the pore size controllable, proved to be detrimental to the formation of a well-defined network structure. This led to a non-uniform or discontinuous copper network. This implies that acetic acid critically retards the electrodeposition of copper.