Molten carbonate fuel cells (MCFCs) are promising high temperature power generating devices. However, unlike solid oxide fuel cells (SOFCs) they utilize a liquid electrolyte which must be immobilized in a porous matrix.In this paper, a slurry composition for lithium aluminate (γ-LiAlO2) matrix was developed and green matrices were subsequently formed by the tape casting method. In order to achieve the desired structure of the matrix (pore size, porosity) γ-LiAlO2 powder was milled in a planetary ball mill for 18 h with a solvent, dispersant and defoamer. After this step, other ingredients were added, including a binder and plasticizer to obtain optimal rheology of the slurry. Cell tests confirmed optimal performance of the matrix compared to the third party reference γ-LiAlO2 matrices. Burned out matrix was characterized by scanning electron microscopy (SEM) and laser diffraction in order to determine the γ-LiAlO2 powder particle size and morphology. The results show that high-energy milling enabled a fine pore structure and high specific surface area of the matrix to be obtained in a relatively short time, compared to conventional fabrication routes. The matrix structure obtained within this study is suitable for high performance operation of MCFC.