To improve the recovery of rare earth elements (REEs) from a refractory ore, this study investigated two different chemical decomposition methods, namely sulfuric acid baking and caustic digestion, with their respective leaching processes. The studied lateritic ore contained goethite (FeOOH) as a major constituent with REEs scattered around and forming submicron grains of phosphate minerals, such as apatite and monazite. Therefore, despite the substantially high content of REEs (3.4% total rare earth oxide), the normal acidic leaching efficiency of REEs reached only 60–70%. By introducing sulfuric acid baking and caustic digestion, the REE-leaching efficiency was significantly improved. After sulfuric acid baking at 2.0 acid/solid ratio and 200 °C for 2 h, the leaching efficiency reached 97–100% in the subsequent water-leaching. When the ore was digested with a solid/liquid ratio of 100 g/L in a 30 wt% NaOH solution at 115 °C and 300 rpm for 3 h, the REE-leaching efficiency of 99–100% was attained at 80 °C using a 3.0 M HCl solution. The correlation between the REE and the Fe-leaching was determined. The improvements in REE-leaching in both methods were mostly attributed to the mineral phase and crystallinity changes of Fe-bearing minerals due to the ore pretreatments. Such findings were also supported by X-ray diffraction and scanning electron microscopy analyses.