Employing luminescence thermometry in the biomedical field is undeniably appealing as many health conditions are accompanied by temperature changes. In this work, we show our ongoing efforts and results at designing novel vehicles for dual-mode thermometry and pH-dependent drug release based on hollow spheres. Hereby for that purpose, we exploit the hollow Y 2 O 3 and Y 2 O 2 SO 4 host materials. These two inorganic hollow phosphors were investigated and showed to have excellent upconversion Er 3+ –Yb 3+ luminescence properties and could be effectively used as optical temperature sensors in the physiological temperature range when induced by near-infrared CW light (975 nm). Further, doxorubicin was exploited as a model anti-cancer drug to monitor the pH-dependent drug release of these materials showing that they can be used for simultaneous thermometry and drug delivery applications.