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Biocatalysis has traditionally been viewed as a field that primarily enables access to chiral centers. This includes the synthesis of chiral alcohols, amines and carbonyl compounds, often through functional group interconversion via hydrolytic or oxidation‐reduction reactions. This limitation is partly being overcome by the design and evolution of new enzymes. Here, we provide an overview of a recently thriving research field that we summarize as biocatalytic alkylation chemistry. In the past 3–4 years, numerous new enzymes have been developed that catalyze sp3 C−C/N/O/S bond formations. These enzymes utilize different mechanisms to generate molecular complexity by coupling simple fragments with high activity and selectivity. In many cases, the engineered enzymes perform reactions that are difficult or impossible to achieve with current small‐molecule catalysts such as organocatalysts and transition‐metal complexes. This review further highlights that the design of new enzyme function is particularly successful when off‐the‐shelf synthetic reagents are utilized to access non‐natural reactive intermediates. This underscores how biocatalysis is gradually moving to a field that build molecules through selective bond forming reactions. [ABSTRACT FROM AUTHOR]