Ce3+ is known to show broad optical emission peaking in the green spectral range. For the stabilization of 3-valent cerium in ceramic phosphors such as calcium scandate CaSc2O4, often co-doping with sodium for charge compensation is performed (Na+, Ce3+ ↔ 2 Ca2+). At the melting point of CaSc2O4 (≈2110°C), however, alkaline oxides evaporate completely and co-doping is thus no option for crystal growth from the melt. It is shown that even without co-doping Ce3+:CaSc2O4 crystal fibers can be grown from the melt by laser-heated pedestal growth (LHPG) in a suitable reactive atmosphere. Reactive means here that the oxygen partial pressure is a function of temperature and p
O2(T) rises for this atmosphere in such a way that Ce3+ is kept stable for all T. Crystal fibers with ≈1 mm diameter and ≤50 mm length were grown and characterized. Differential thermal analysis (DTA) was performed in the pseudo-binary system CaO–Sc2O3, and the specific heat capacity c
(T) of CaSc2O4 was measured up to 1240 K by differential scanning calorimetry (DSC). Near and beyond the melting point of calcium scandate significant evaporation of calcium tends to shift the melt composition towards the Sc2O3 side. Measurements and thermodynamic calculations reveal quantitative data on the fugacities of evaporating species.