Nanoporous gold (npAu) was tested as a catalyst for oxidations of various benzylic sp3-carbon positions in 9H-fluorene derivatives and similar hydrocarbons using tertbutyl hydroperoxide (TBHP) as an oxidant. The silver content in the npAu catalyst had a major influence on the overall conversion: Lower silver amounts (0.53 mol%) led to higher conversions, whereas higher amounts of silver increasingly resulted in the disproportionation of TBHP as a competing reaction. Because residual silver from the bulk alloy was oxidized by TBHP and leached into the solution during the reaction, the Ag content diminished over time. Therefore, the recycling of the catalyst had a positive effect on the conversion after each use. Using electron paramagnetic resonance (EPR) spectroscopy, the formation of radicals from TBHP by npAu was evidenced indicating a radical-based reaction mechanism which was further elucidated by NMR spectroscopic and GC-MS (trace) product analysis. Subsequent oxidations of benzylic sp3-carbon positions gave good to excellent conversions and chemoselectivities featuring npAu as a suitable catalyst for such reactions.