The spreading of liquid alkalies over solid surfaces has important applications in painting, coatings, lubrication, and petroleum tertiary recovery. The role of the vapor-phase mass transport accompanying liquid spreading has not been well studied because it is difficult to separate the contributions from the liquid spreading and the vapor-phase transport that occurred at the same time. We used the engineered surface patterns to study the vapor-phase mass transport during liquid spreading. First, we fabricated several hydrophilic, carboxylic acid-terminated patterns (OTSpd) oil a hydrophobic, methyl-terminated octadecyltrichlorosilane (OTS) surface. These OTSpd patterns did not connect to each other. Next, we let an alkane drop spread within one OTSpd pattern. The liquid alkane could not spread to other OTSpd patterns because OTS separated them; however, the alkane molecules in the vapor phase Could migrate and adsorb on other OTSpd patterns. Therefore, the contributions from the liquid spreading and the vapor-phase transport were separated and could be investigated independently. We found that during the spreading of the liquid alkane, mass transport through the vapor phase cannot be ignored. Alkane molecules adsorbed on the OTSpd surface with their backbones parallel to the surface in the First few layers. Additional alkane molecules adsorbed on these parallel layers to form the seaweed-shaped layers in which the alkane molecules stood up. Our study showed that the parallel layers formed from the vapor-phase mass transport before the liquid alkane spread. Therefore, the liquid alkane does not spread over the more strongly binding OTSpd surface. It actually spreads over the parallel alkane layer, which formed from its own vapor.