Structurally isomeric octanol interfacial systems, water/vapor, 3-octanol/vapor, n-octanol/vapor, 3-octanol/water, n-octanol/water, and mixed 3-octanol+noctanol/water are investigated using molecular dynamics simulation techniques. The present study is intended to investigate strongly associated liquid/liquid interfaces, probe the atomistic structure of these interfaces, and study the effects of interfaces on mixtures. The molecules were initially placed randomly into a box a to minimize bias within the initial conditions and to fully sample the structural conformations of the interface. During equilibration an interface formed via phase separation and resulted in a slab geometry with a molecularly sharp interface. However, some water molecules remained within octanol phase with a mole fraction of 0.12 after equilibration. Our results support the hypothesis of an ordered interface only 1 or 2 molecular layers deep before bulk properties are reached for both the 3-octanol and water systems. However, in contrast to most other interfacial systems studied by molecular dynamics simulations, the n-octanol interface extends for several molecular layers. The octanol hydroxyl groups form a hydrogen bonding network with water which orders the surface molecules toward a preferred direction and produces a hydrophilic/hydrophobic layering. The ordered n-octanol produces an oscillating low-high density of oxygen atoms out of phase with a high-low density of carbon atoms, consistent with an oscillating dielectric. In contrast, the isomeric 3-octanol has only a single carbon rich layer directly proximal to the interface, which is a result of the different molecular topology. Both 3-octanol and n-octanol roughen the water interface with respect to the water/vapor interface. The "wet" octanol phases, in the octanol/water systems reach bulk properties in a shorter distance than the "dry" octanol/vapor interfaces