Oxygenases-catalyzed reductive activation of molecular oxygen and incorporation of O atoms into an organic molecule is undoubtedly one of the most attractive research areas. Typically, these oxygenation reactions proceed with high selectivity and reactivity, which is seldom found in its "biomimetic" chemocatalytic counterparts. Furthermore, enzymatic oxygenation can avoid undesired overoxidation, which is frequently observed in (industrial) chemical transformation. Therefore, it is not surprising that tremendous attention has been paid to enzymatic oxygenation. Their application in organic synthesis has been steadily growing over the years. The goal of the present Review is to provide a handy reference for chemists interested in using homogeneous oxygenase catalysis and those interested in discovering new types of biomimetic oxidations and oxygenations with dioxygen. In this Review, we will review the recent advances in in homogeneous oxygenase catalysis to reveal the great achievements and potentials in this field.