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We have performed a spectroscopic study of ErxY1-x[(p-CF3-C6F4)2PO2]3aimed at understanding nonradiative de-excitation mechanisms. These fluorinated compounds have a long lifetime for the erbium 4I13/2→ 4I15/2emission at λ ∼ 1540 nm, but the lifetime increases with decreasing x. We have studied the lifetime as a function of morphology, temperature, and high hydrostatic pressure. We have demonstrated the occurrence of energy migration and calculated the corresponding activation energy. Moreover, using high pressure techniques, we provide evidence that cross-relaxation involving energy transfer from an excited erbium in the 4I13/2promoting a neighbor in the same state to 4I9/2is the dominant mechanism at ambient conditions for short erbium−erbium distances. The model explains the observed dynamics of excited states in the series and is tested against the Yb[(p-CF3-C6F4)2PO2]3compound. [ABSTRACT FROM AUTHOR]