A new method to tune both phosphorescence emission intensity and spectroscopic colors based on the alternatively structured host/guest multilayer thin films prepared by the spin-assisted LbL deposition is presented. Their emission characteristics are demonstrated with pairs of positively charged Ir-PEI complexes as guests and negatively charged CBZ-PAA as hosts. The phosphorescent emission of Ir-PEI complexes is enhanced by the energy transfer from the host to the guest and, additionally, this energy transfer can be finely tuned by the insertion of spacer layers between the phosphorescent donor and acceptor layers to vary the emission intensity as well as to render different emission colors.