Low-temperature co-fired ceramic (LTCC) is an important material in the production of ceramic multilayer structures. Large and complex multilayer structures are usually fired at higher temperatures and/or longer firing times compared to the relatively thin LTCC tapes. The firing conditions of LTCC determine the phase composition and the microstructure, which both influence the physical characteristics, such as the mechanical and thermal properties. In this work the effect of the phase composition on the biaxial flexural strength and the temperature coefficient of expansion of the DuPont 951 LTCC is presented. The samples were fired at different temperatures and times to obtain different phase compositions. The phase composition, especially the mass fraction of anorthite, was correlated with the biaxial flexural strength and the thermal coefficient of expansion (TCE). A very long firing time, i.e., 100h at 800 °C, yields, apart from crystalline anorthite, the cristobalite phase. The anorthite that crystalizes from the glass phase in a dense LTCC material changes the crack-propagation mechanism and improves the biaxial flexural strength of the material. The major change in the biaxial flexural strength is observed when the anorthite phase appeared. The increasing mass fraction of anorthite does improve the biaxial flexural strength less drastically. With the increasing mass fraction of the anorthite, decreases of the TCE of the material and a small decrease of the density of the LTCC material occur.