Using polarization sensitive ultrafast transient absorption spectroscopy we have studied energy transfer and excited state relaxation pathways in a tetranuclear transition metal [(osmium)(ruthenium)3] polypyridine complex. Contrary to the generally accepted picture of transition metal complex photochemistry we find that ultrafast energy transfer (< or =60 fs) occurs from the excited singlet MLCT state of the peripheral Ru-chromophores to the central Os-core, in efficient competition with intersystem crossing. Energy transfer between relaxed triplet MLCT states is more than an order of magnitude slower (600 fs).