Multicomponent Bi-Mo-Fe-Co oxide catalysts prepared via flame spray pyrolysis were tested for selective propylene oxidation, showing high conversion (>70%) and selectivity (>85%) for acrolein and acrylic acid at temperatures of 330 °C. During extended time-on-stream tests (5–7 days), the catalysts retained high activity while undergoing diverse structural changes. This was evident on: (a) the atomic scale, using powder X-ray diffraction, Raman spectroscopy, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy; and (b) the microscopic scale, using synchrotron X-ray nanotomography, including full-field holotomography, scanning X-ray fluorescence, and absorption contrast imaging. On the atomic scale, sintering, coke formation, growth, and transformation of active and spectator components were observed. On the microscopic scale, the catalyst life cycle was studied at various stages through noninvasive imaging of a ~50-µm grain with 100-nm resolution. Variation of catalyst synthesis parameters led to the formation of notably different structural compositions after reaction. Mobile bi ... mehrsmuth species formed agglomerates of several hundred nanometres and segregated within the catalyst interior. This appeared to facilitate the formation of different active phases and induce selectivity for acrolein and acrylic acid. The combined multiscale approach here is generally applicable for deconvolution of complex catalyst systems. This is an important step to bridge model two-component catalysts with more relevant but complex multicomponent catalysts.