Single components and multicomponent of R-phycoerythrin (R-PE ), Cphycocyanin (C-PC ) and allophycocyanin(APC) LB multilayers were prepared. The three phycobiliproteins in the LB films were orderly oriented as in the natural phycobilisomes. The absorption and fluorescence spectra remainedsimilarly to these in their aqueous solutions. The phenomenon of excitation energy transfer among R-PE, C-PC and APC in their stacking LB multilayers were observed through steady-state fluorescence spectral measurements and spectral deconvolutions. From the quenching degree of R-PE fluorescence, the efficiency of energy transfer from R-PE through C-PC to APC in their stacking LB multilayers was calculated to be 51%.