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This book deals, the rare earth ions (RE3+) are used to probe the local structural variations in the host glass matrices, because of their unique spectroscopic properties resulting from the 4f-4f intra-configurational radiative transitions. Glasses containing rare earths as luminescent centers are of great interest due to their unique optical, electrical and magnetic properties. In the development of RE3+ ions doped optical devices; the host glass plays a very important role. Photoluminescence properties of RE3+ ions change drastically from host to host as well as by the variation of their concentration in the host. This behavior of the RE3+ ions has made the researchers to search for novel materials with different compositions to investigate and reveal their behavior in different hosts with various concentrations. In order to identify new optical devices and to propose possible excitation schemes, active research has to be carried out for the search of new hosts doped with RE3+ ions. In view of this, it is proposed to investigate certain RE3+ ions namely Nd3+, Sm3+, Dy3+ and Er3+ ions doped borate based tellurium calcium zinc niobium oxide (TCZNB) glasses.