Octachloro zinc phthalocyanine networks oil Ag(111) have been used as host Structures for the insertion of penta-tert-butylcorannulene (PTBC) molecules. At ambient temperature, the resulting coassemblies generally present lines or chessboard structure, depending on the PTBC coverage. In this paper, it is shown that the annealing of these Structures leads to the formation of novel networks in which the interplay of both Molecules plays I major role. The presence of PTBC is also found to prevent the phase transition that generally appears in the phthalocyanme host lattices. PTBC molecules show two different positions with respect to the phthalocyanine networks when the observations ire conducted at 4.6 K while at liquid nitrogen temperature (77 K), some of them appear with six bump) features. Calculations Suggest that this originates from the rotation barriers of the PTBC molecules in the host molecular structures. Finally, evaporation of the PTBC oil a cooled Substrate shows that the PTBC adsorbs oil top of the Zn atom of the phthalocyanine and presents a nonuniform contrast due to the peculiar geometry of the PTBC/phthalocyanine structure.