The strategic importance of tantalum and its scarcity in Europe makes its recovery from low grade deposits and tailings interesting. In Penouta, the contents of Ta and Sn in old tailings from an Sn mine are of economic interest. Due to the relatively low grade of Ta of around 100 ppm, a detailed study of the mineralogy and liberation conditions is necessary. In this study, the mineralogy and the liberation characteristics of Sn and Ta ores of the Penouta tailings were investigated and compared with the current leucogranite outcropping ores. The characterization was conducted through X-ray diffraction, scanning electron microscopy, and electron microprobe. In addition, automated mineralogy techniques were used to determine the mineral associations and liberation characteristics of ore minerals. The grade of the leucogranite outcropping was found to be about 80 ppm for Ta and 400 ppm for Sn, and in the tailings used for the liberation study, the concentrations of Ta and Sn were about 100 ppm Ta and 500 ppm Sn, respectively. In both, the leucogranite outcropping and tailings, the major minerals found were quartz, albite, K-feldspar, and white mica. Ore minerals identified were columbite-group minerals (CGM), microlite, and cassiterite. The majority of CGM examined were associated with cassiterite, quartz, and muscovite particle compositions and cassiterite was mainly associated with CGM, quartz, and muscovite. The liberation size was 180 µm for CGM.