Mechanistic investigations at the density functional theory level of organic and organometallic reactions in solution are now broadly accessible and routinely implemented to complement experimental investigations. The selection of an appropriate functional among the plethora of developed ones is the first challenge on the way to reliable energy barrier calculations. To provide guidelines for the choice of an initial and reliable computational level, the performances of commonly used non‐empirical (PBE, PBE0, PBE0‐DH) and empirical density functionals (BLYP, B3LYP, B2PLYP) were evaluated relative to experimental activation enthalpies. Most reactivity databases to assess density functional performances are primarily based on high level calculations, here a set of experimental activation enthalpies of organic and organometallic reactions performed in solution were selected from the literature. As a general trend, the non‐empirical functionals outperform the empirical ones. The most accurate energy barriers are obtained with hybrid PBE0 and double‐hybrid PBE0‐DH density functionals, both providing similar performance. Regardless of the functional under consideration, the addition of the GD3‐BJ empirical dispersion correction does not enhance the accuracy of computed energy barriers.