Transition metal oxide-containing glasses (TMOGs) have special and unique optothermal properties. One can verify how the optical, thermal, and thermoelectric properties vary with composition. This work tries to give more insight into the subject of the thermal stability and its effect on the optothermal properties of some vanadate-tellurite oxide glasses. In other words, optical and thermal characterization of such glassy systems can be investigated versus the composition with the aim of finding the more potential candidates in optical applications. Moreover, besides thermal stability, different parameters such as elastic moduli, optical bandgap, molar volume (Vm), oxygen molar volume ( V∗O ), oxygen packing density (OPD), molar refraction (Rm), metallization criterion (M), and the concentration of non-bridging oxygen ions (NBOs) can be evaluated and discussed as the most important factors on the properties and applications of a material. In brief, optical applications (such as active material in optical fibers) of oxide glasses need the high thermal stable glasses with narrower bandgap. It should be noted that any suggestion for optical applications needs precise determination of optical properties such as energy bandgap, which affect the evaluation of other related optical parameters and so in optical device manufacturing and applications; in the case of bandgap determination, derivative absorption spectrum fitting method (abbreviated as DASF) has been recently proposed; this method is briefly introduced in this work. Also, such thermal stable glasses with good thermoelectric properties are promising materials which can be used in solar cells and photovoltaic (PV) panels as heat pumps to elevate the PV efficiency. An attempt has been made to discuss these subjects, giving more light in the field of optothermal aspects.