It is well known that asphaltene molecules play a significant role in stabilizing emulsions of water in crude oil or diluted bitumen solutions. Molecular dynamics simulations were employed to investigate the aggregation and orientation behaviors of asphaltene molecules in a vacuum and at various water surfaces. Two different continental model asphaltene molecules were employed in this work. It was found that the initially disordered asphaltenes quickly self-assembled into ordered nanoaggregates consisting of several molecules, in which the aromatic rings in asphaltenes were reoriented to form a face-to-face stacked structure. More importantly, statistical analysis indicates that most of the stacked polycyclic aromatic planes of asphaltene nanoaggregates tend to be perpendicular to the water surface. If the asphaltene molecules are considered as “stakes”, then the asphaltene nanoaggregate can be regarded as a “fence”. All the fence-like nanoaggregates were twined and knitted together, which pinned them perpendicularly on the water surface to form a steady protective film wrapping the water droplets. The mechanism of stabilization of the water/oil emulsions is thereby well understood. Demulsification processes using a chemical demulsifier were also studied. It was observed that the asphaltene protective film was destroyed by a demulsifier of ethyl cellulose molecules, leading to exposure of the water droplet. The results obtained in this work will be of significance in guiding the development of demulsification technology.