Regular square, wirelike, quadrate, and rodlike nanocrystal arrays of Cd2+, Hg2+, or Ag+ metal-cation-mediated sandwich-type mixed (phthalocyaninato) [5,10,15,20-tetrakis(4-pyridyl)poprhyrinato] cerium(III) double-decker complex Ce(Pc)(TPyP) have been successfully prepared at the water-chloroform interface. The nanocrystal growth processes were monitored by transmission electron microscopy (TEM), which reveals that different morphologies of nanocrystals have been fabricated from double-decker molecules connected by different kinds of metal cations, forming coordination polymers. These nanoscaled coordination polymers were characterized by FT-IR spectra and energy-dispersive X-ray spectra (EDS). EDS results clearly revealed the elements of the nanocrystals and the FT-IR spectra give evidence for the coordination interaction between the double-decker molecules and metal cations. The UV-vis absorption spectrum indicates the formation of J-aggregates of the double-decker molecules in the nanocrystals formed.