We present a systematic scanning tunneling microscopic study on the mixing behavior of molecules (DBAs) with different alkyl substituents at the solid-liquid interface to reveal the phase behavior of complex systems. The phase behavior of binary mixtures of alkylated DBAs at the solid-liquid interface can be predicted by the 2D isomorphism coefficient. In addition, we also investigated the influence of coadsorption of template molecules on the phase behavior of DBA mixtures. Coadsorption of these molecules significantly promotes mixing of DBAs, possibly by affecting the recognition between alkyl chains. Monte Carlo simulations prove that the 2D isomorphism coefficient can predict the phase behavior at the interface. These results are helpful for the understanding of phase behavior of complex assembling systems and also for the design of programmable porous networks and hierarchical architectures at the solid-liquid interface.