Controlling the orientations of molecules in self-assembled monolayers on surfaces is an effective means to construct high quality organic devices. Herein, we utilize linear polymer-modified step edges as a simple and peculiar template for regulating the subsequent self-assembly of alkane molecules (n-C32H66). With this strategy, all the alkane molecules orientate along the step edge ([011] directions). Combining with systematical DFT calculations, we demonstrated that it is the van der Waals interactions between the molecules that leads to (1) the initially adsorbed alkane monomers lie parallel to the polymers; (2) the adjacent alkane molecules show a parallel configuration. Since the polymers anchor on the surface along an exclusive [011] direction, all the adsorbed molecules in the self-assembly islands are regulated along the [011] directions as well.