LTCC (Low Temperature Co-fired Ceramics) being the most advantageous technology towards the multilayer substrates for various applications, demands an extensive study of its raw materials. In the present work, a series of CuxMg1-xNb2O6 (x=0,0.4,0.6,1) has been prepared using sol-gel synthesis route and sintered at a temperature of 900°C to study its applicability for LTCC technology as the firing temperature is 900°C in this technology. The phase formation has been confirmed using X-ray Diffraction. Thermal properties like thermal conductivity and thermal expansion being very important aspect as the former defines the heat flow to avoid thermal instability in layers and the later provides the dimensional congruency of the dielectric material and the conductors, are studied here over high temperature up to the firing temperature. Although the values are quite satisfactory from substrate requirement point view, results have shown anomaly over temperature. The anomalous thermal behavior has been further analyzed using TG-DTA.