Herein, we demonstrate operando photoelectron photoion coincidence (PEPICO) spectroscopy as a pivotal technique for evidencing unprecedented mechanistic insights by isomer-selective radical detection within complex hydrocarbon-functionalization reaction networks, such as those of catalyzed propane oxychlorination and oxybromination. In particular, while the oxychlorination is surface-confined, we show that in oxybromination alkane activation follows a gas-phase reaction mechanism with evolved bromine and bromine radicals, favoring 2-propyl over 1-propyl radical formation, as evidenced by isomer-selective threshold photoelectron analysis. Furthermore, we provide new mechanistic insights into the cracking and coking pathways that are observed in oxybromination. The first entails propargyl radical formation from consecutive hydrogen abstraction of propyl radicals, ultimately yielding benzene. The second originates from C-C bond cleavage in propane to ethyl and methyl radicals, which produce CH4 and C2H4, or undergo chain-growth reactions, forming C4-C6 species.