After coating 20 Yb/2 Er:NaGdF4 core nanocrystals with a NaYbF4 shell, upconversion emission of the rare earth ions weakens. So far, the exact reason for this phenomenon is still unclear due to lack of the direct evidence. In this report, a core@shell@shell sandwich-like structure is designed and fabricated to investigate this phenomenon. We find that high Yb(3+) concentration in the shell has mainly two adverse impacts: it promotes not only the deleterious back energy transfer from Er(3+) in the core to Yb(3+) in the shell but also the energy transfer from Yb(3+) in the core to Yb(3+) in the shell. To obtain nanocrystals with high upconversion efficency, appropriate Yb(3+) concentration should be introduced into the shell or the transition layer.