LiCaAlF₆ is a versatile host material. Applications of this host asscintillation detector and solid state laser have been reported quite frequently. Thermoluminescence studies on LiCaAlF₆:Eu have also been reported. They are, however, not consistent. The glow curve structure depends on the synthes is route. At least two glow peaks are observed, around180°C and 240°C. Effects of co-doping on the glow curve are reported. Co-doping with y (0.5mol%) suppresses the 240°C peak and increases the intensity of 180°C peak nearly 3 fold and shifts it to slightly higher temperature of 190°C. Co-doping with La(0.8mol%), on the other hand, removes180°C peak and intense peak at 240°C can be observed. Thus co-doping produces a relatively simple glow curve with only one dominant peak. LiCaAlF₆:Eu phosphor also shows intense optically stimulated luminescence (OSL). The OSL sensitivity of LiCaAlF₆:Eu co doped with Y is about 7 times that of commercially available Al₂O₃:C. Other OSL properties useful for dosimetry applications are also reported in this paper.