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Hydrogenases are metalloenzymes central to hydrogen metabolism, where they catalyze the oxidation and formation of molecular hydrogen. Herein we will focus on the so-called [FeFe] hydrogenases and their related molecular mimics. With regards to the enzyme, emphasis will be placed on the molecular details of their organometallic cofactor and active-site architecture as well as the catalytic mechanism. Subsequently, the extensive efforts during the last two decades dedicated to the preparation of molecular systems mimicking structural and reactivity aspects of these enzymes are summarized. Finally, we will discuss work related to the preparation of “semi-synthetic” [FeFe] hydrogenases, incorporating synthetic cofactors.