Gold nanoparticles offer tremendous potential in the areas of nanoelectronics, bio- and chemosensors, and catalysis. However, before these applications are realized, the surface functionality of nanoparticles must be better controlled. Our lab has recently reported a novel synthetic approach for making monofunctionalized nanoparticles through a solid phase place exchange reaction. Monofunctionalized gold nanoparticles may also be prepared through a solution phase place exchange reaction. In this study, we compared the efficiency of these two separate approaches toward controlled functionalization of gold nanoparticles by (1)H NMR, Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) analysis. We found that the solid phase place exchange approach is much more efficient at producing monofunctionalized gold nanoparticles. (1)H NMR data were used to give a semiquantitative count of substituted bifunctional ligands, and FT-IR spectra supported these findings. Furthermore, we used a diamine coupling reaction of nanoparticles to show the presence of single or multiple functional groups on the nanoparticle surface by TEM analysis.