AbstractWe introduce a novel instrument combining femtosecond pump-probe spectroscopy and confocal microscopy for spatio-temporal imaging of excited-state dynamics of phase-separated polymer blends. Phenomena occurring at interfaces between different materials are crucial for optimizing the device performances, but are poorly understood due to the variety of possible electronic states and processes involved and to their complicated dynamics. Our instrument (with 200-fs temporal resolution and 300-nm spatial resolution) provides new insights into the properties of polymer blends, revealing spatially variable photo-relaxation paths and dynamics and highlighting a peculiar behaviour at the interface between the phase-separated domains.