The adsorption behaviour of nanoparticles at the polydimethylsiloxane droplet/water interface and the influence of particle hydrophobicity, droplet deformability, and the surface electrical properties of both particles and droplets (as controlled by pH and salt concentration) are reported. Adsorption of hydrophilic nanoparticles is weakly influenced by pH but significantly influenced by salt addition, whereas for hydrophobically modified nanoparticles a balance of hydrophobic and electrostatic forces controls adsorption over a wide range of pH and salt concentrations. The relationships between the adsorbed nanoparticle layer structure, droplet stability, and the oil-to-water transport properties have also been elucidated.