The excited-state dynamics of widely used luminescence centers Yb3+ and Er3+ embedded in special core–shell–shell (CSS) structured NaYF4/NaYF4:Yb3+,Er3+/NaYF4 nanoparticles (NPs) are investigated. The CSS multi-layer structure is confirmed by transmission electron microscopy and the nonradiative relaxation coefficient (W) is investigated by time-resolved spectroscopy. The effect of surroundings on W for certain energy levels (Er3+: 2H11/2/4S3/2 and Yb3+: 2F5/2) is identified and W decreases exponentially upon increasing the shielding shell thickness of the prepared CSS NPs. In addition, it has been confirmed that the luminescence centers are nearly immune to surrounding quenching when the shielding shell thickness is boosted to ca. 4 nm.