By molecular dynamics simulations, we have studied the hydrophilic-hydrophobic interface between water and n-hexane liquid phases. For all temperatures studied our computed interfacial tension agrees very well with the experimental value. However, the interfacial width calculated from capillary wave theory systematically overestimates the width obtained from fitting either the total density or composition profile. We rationalize the applicability of capillary wave theory for our system by reconsidering the usual value taken for the correlation length. This is motivated by the presence of order at the interface. Possible implications for recent experimental studies on the structure of model alkane-water interfaces are discussed, including the significance of the intrinsic width parameter. (C) 2004 American Institute of Physics.