Luminescent zeolites exchanged with two distinct and interacted emissive ions are vital but less-studied for the potential applications in white light emitting diodes, solar cells, optical codes, biomedicine and so on. Typical transition metal ion Mn2+ and lanthanide ion Yb3+ are adopted as a case study via their characteristic transitions and the interaction between them. The option is considered with that the former with d-d transition has a large gap between the first excited state 4T1 and the ground state 6A1 (normally >17,000 cm-1) while the latter with f-f transition has no metastable excited state above 10,000 cm-1, which requires the vicinity of these two ions for energy transfer. The results of various characterizations, including BET measurement, photoluminescence spectroscopy, solid-state NMR, and X-ray absorption spectroscopy, etc., show that Yb3+ would preferably enter into the zeolite-Y pores and introduction of Mn2+ would cause aggregation of each other. Herein, cation-cation repulsion may play a significant role for the high valence of Mn2+ and Yb3+ when exchanging the original cations with +1 valence. Energy transfer phenomena between Mn2+ and Yb3+ occur only at elevated contents in the confined pores of zeolite. The research would benefit the design of zeolite composite opto-functional materials.