One major challenge of future sustainable photochemistry is to replace precious and rare transition metals in applications such as energy conversion or electroluminescence by earth‐abundant, cheap, and recyclable materials. This involves using coordination complexes of first row transition metals such as Cu, Cr, or Mn. In the case of iron, which is attractive due to its natural abundance, fundamental limitations imposed by the small ligand field splitting energy have recently been overcome. In this review article, we briefly summarize the present knowledge and understanding of the structure‐property relationships of Fe(II) and Fe(III) complexes with excited state lifetimes in the nanosecond range. However, our main focus is to examine to which extent the ultrafast spectroscopy methods used so far provided insight into the excited state structure and the photo‐induced dynamics of these complexes. Driven by the main question of how to spectroscopically, i. e. in energy and concentration, differentiate the population of ligand‐ vs. metal‐centered states, the hitherto less exploited ultrafast vibrational spectroscopy is suggested to provide valuable complementary insights.