We describe a novel and versatile method for the fabrication of poly(ferrocenylsilane) (PFS) based microspheres using microfluidics. Cross-linked microgel particles were obtained by UV-induced crosslinking of precursor droplets. By variations in the substitution of the silane units of PFS, organogel as well as hydrogel particles were prepared. Applications of these redox active microspheres to form in situ Ag nanoparticles, as well as loading and release of guest molecules were demonstrated.