Recent interest in the use of nanoparticles in emulsion stabilization has driven increased efforts to understand how the characteristics of the particles influence the emulsion properties. While it is clear that the contact angle and wettability must play significant roles in determining the type of emulsion formed, it is not straightforward to measure the contact angle of a nanoparticle. In this paper, we compare multiple techniques for characterizing the water–air contact angle of silica nanoparticles while systematically varying the hydrophobicity of the nanoparticles using silanization. We then compare the performance of the particles in decane/water emulsions. While the heat of immersion measured by microcalorimetry is found to provide the best method for discriminating between the wettability of the particles, the fraction of surface covered by the silane groups was observed to affect the structure of the emulsion more profoundly than the differences in the contact angles of the particles. Furthermore, we find that the phase of initial dispersion is extremely influential in determining the resulting emulsion type and droplet size.