The structures of aqueous M4+(aq) and MF3+(aq), where M is uranium(IV) or thorium(IV), have been determined by L-III edge EXAFS using data from solutions of 1.5 M HClO4 in which the M(IV) concentrations ranged from 0.03 to 0.3 M. A least-squares refinement of the data for the aqua ions indicated 10.8 +/- 0.5 water molecules in the first hydration sphere of both ions and M-O bond distances for U(IV) and Th(IV) of 2.42 +/- 0.01 and 2.45 +/- 0.01 Angstrom, respectively. By considering both previous structure information and the EXAFS data, we selected N = 10 +/- 1 as the most likely coordination number of both M(IV) aqua ions. EXAFS measurements from acidic aqueous uranium(IV) and thorium(IV) solutions containing fluoride show that large changes in the first coordination sphere occur. The experimental data indicates an asymmetrical distribution of the distances, probably as a result of differing M-F and M-O bond lengths. These can be described by a model that contains two different bond distances,one M-F distance at 2.10 Angstrom and one M-O distance at 2.45 Angstrom for U(IV); for Th(IV), the corresponding distances are 2.14 and 2.48 Angstrom. The total coordination number in this model is unchanged from the aqua ions, i.e., 10 +/- 1.