Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to < 10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.