There is a need to develop new solid-phase adsorbents to extract elements from the coal ash. High surface area carbon adsorbents are remarkably good at adsorption of rare earth elements and have good stability in acidic media. A high surface area (1162 m2/g), surface-oxidized microsphere flower carbon (MFC-O) has been prepared for the extraction of rare earth elements as well as thorium and uranium. MFC-O exhibits outstanding distribution coefficients up to kd = 1.2 × 106 for thorium, uranium, and rare earth elements. It was found that thorium and uranium can be separated from the rare earth elements by adjusting the pH. The maximum extraction capacity (71.3 mg/g) was performed up to 88 ppm with 18 competitive elements (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U), and element recovery was >85%. A coal ash sample (NIST SRM 1633c) with a known concentration of elements (Na, Ca, Al, Si, Fe, Sc, La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu, Th, and U) was leeched resulting in 45% Ce recovery. The leeched solution from NIST 1633c was then mixed with MFC-O for Ce extraction of 74%, Na (17%), Ca (13%), Al (24%), Si (41%), and Fe (17%). The binding properties of MFC-O show that it is an attractive material for the selective extraction of rare earth elements from coal ash.