AbstractThe thermal decomposition of Zr(acac)4 is studied in a SiC-microreactor on the micro-second time scale. By utilizing synchrotron radiation and photoelectron photoion coincidence spectroscopy, six important zirconium intermediates, as for instance Zr(C5H7O2)2(C5H6O2), and Zr(C5H6O2)2, are identified in the gas phase for the first time. The adiabatic ionization thresholds of intermediately formed zirconium species are estimated and the main products of their thermal decomposition, acetylacetone, acetylallene and acetone are characterized unambiguously and isomer-selectively. Based on all detected intermediates, we deduce the predominant pyrolysis pathways of the precursor in the temperature range from 400 to 900 K. Our findings are complemented by numerical simulations of the flow field in the microreactor, which show that the choice of dilution gas significantly influences the temperature profile and residence times in the microreactor, such that helium provides a more uniform flow field than argon and should preferentially be used. Graphical abstract Using a soft ionization method coupled to velocity map imaging (VMI), leads to valuable insights in the thermal decomposition of Zr(C5H7O2)4, used in the synthesis of functional nanomaterials and ceramic coatings. Thanks to the use of a microreactor, important gas