X-ray absorption fine structure (XAFS) is used to determine the structure of the rhodium cluster present during the catalyzed dehydrocoupling of amine boranes under operando conditions. We show how a variety of XAFS strategies can be used in combination with other analytical methods to differentiate homogeneous from heterogeneous systems. Analysis of the in situ XAFS spectra using a series of amine boranes (NH3BH3, R2NHBH3, and RNH2BH3 where R = methyl, isopropyl, ted-butyl, and cyclohexyl) and rhodium catalyst precursor compounds (including chloro-(1,5-cyclooctadiene)rhodium (I) dinner, bis(1,5cyclooctacliene)rhodium (I) trifluoromethanesulfonate, chlorodicarbonylrhodium (I) dimer, dichloro(pentamethylcylcopentadienyl)rhodium (III) dimer, hexarhodium hexaclecacarbonyl, and tetrarhodiurn dodecacarbonyl) strongly suggest that the active catalyst species for this reaction is a homogeneous rhodium complex. Rhodium clusters containing four or six rhodium atoms (Rh4-6) bound to amine boranes are observed as the major (> 99%) rhodium containing species during and after the catalyzed anaerobic clehydrocoupling. During the later stages of the reaction a nonmetallic rhodium complex precipitates in which individual Rh4-6 clusters likely form polymer chains ligated by the reaction products that have two or more ligating sites. The best fits of the XAFS data, using ab initio calculations of FEFF theory, show that the major rhodiurn species (80%) has each rhodium atom directly bound to three rhodium atoms with an observed bond distance of 2.73 angstrom and to two boron atoms at 2.10 angstrom. A minor (20%) rhodium species has each rhodiurn atom bound to four rhodium atoms with a bond distance of about 2.73 angstrom and a single rhodiurn atom at a nonbonding distance of 3.88 angstrom. No metallic rhodium was observed at any time during the anaerobic reaction.