The interfaces of water micro- and nanodroplets drive environmental, medical, catalytic, biological, and chemical biphasic processes. The interfacial droplet structure and electrostatics greatly determine the reactivity and efficiency of these processes. Droplet interfacial properties are elusive and generally inferred from bulk measurements and are therefore anything but exact. Here, we quantify the interfacial ordering of water and the electrostatic surface potential of nanoscale water droplets in an apolar liquid using angle-resolved polarimetric second-harmonic scattering. We also present a method to determine the amount of free charges in the hydrophobic phase, reaching a sensitivity that is 3 orders of magnitude better than conductivity measurements. Investigating the structural and surface electrostatic changes induced by AOT surfactant adsorption, we find that both the hydrogen bonding as well as the electrostatics strongly depend on the surfactant concentration. Above the critical micelle concentration, the interface mediates micelle self-assembly.