We present a systematic scanning tunneling microscopy study on the 2D self-assembly of pentagonal shaped macrocycles at the liquid/solid interface to gain insight about 2D pentagonal molecular crystallization. Macrocycles with alkyl ester groups form an anti-parallel type linear pattern mainly via favorable intermolecular interactions between the interdigitated alkyl chains at the 1,2,4-trichlorobenzene (TCB)/graphite interface. On the other hand, at the TCB/Au(111) interface, they showed a random pattern and an anti-parallel type linear pattern. The selection between both motifs is ascribed to the balance between the intermolecular and molecule-substrate interactions. Most interestingly, the parent molecule forms dense anti-parallel and parallel linear patterns reflecting the intrinsic pentagonal core shape. Moreover, bright and mobile spots were often observed in the networks to occupy free spaces, including the cavity of the macrocycles, which we attribute to a co-adsorbed solvent molecule or Au ion.