The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris(10-carboxydecyloxy)benzene(TCDB) template through scanning tunneling microscopy(STM). STM images of molecular adlayers of zinc tetraphenylporphyrin(Zn TPP), zinc phthalocyanine(Zn Pc), and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1:1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions. The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris (10-carboxydecyloxy) benzene (TCDB) template through scanning tunneling microscopy (STM). STM images of molecular adlayers of Zn tetraphenylporphyrin (Zn TPP), zinc phthalocyanine (Zn Pc), and their mixtures were reported. Zn TPP and Zn Pc can spontaneously form highly ordered structures with a 1: 1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc-DPP-Zn TPP and Zn Pc-DPE-Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be linked by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structures are obtained for the Zn Pc-DPE-Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination throug h non-covalent interactions.