In both rare earth physics and chemistry, the study of luminescencent rare earth doped solid state materials is an interesting area for research. Among the lanthanide group, europium is a special element and exhibits the property of valence fluctuation besides the common properties of rare earth elements. The use of Eu3+ ion has been immense in color television, flat panel displays, cathode ray tube and fluorescent powders of three primary colors due to its property of red light emission [1–3]. Hence for the fabrication of white LEDs it is vital to develop more efficient red emitting phosphors that are suitable for phosphor converting LED’s. Due to the high quantum efficiency, water resistance, low cost, excellent chemical and thermal stability there has been an extensive investigation on silicate-based phosphors. Materials including Eu3+, are the most interesting luminophores for red phosphors which are widely used as a red-emitting activator through the 5D0?7F2 transition at about 614 nm. The transition metal ions usually are co-doped as sensitizers to enhance the red emission intensity of Eu3+ [4,5]. Further, Calcium silicate (CaSiO3) also known as wollastonite, is a good matrix of luminescent material. CaSiO3 possesses a higher luminous efficiency after it is doped with activator ions. Over the past two decades, researchers started investigating the luminescent material with matrix CaSiO3, that has led to wide use of silicate based materials in vast engineering fields[6–9].