Sampling potential energy surfaces (PES) is pivotal for understanding chemical structure, energetics and reactivity and is of special importance for complex condensed‐phase systems. Until recently such simulations based on electronic structure theory have been performed only by density functional theory and semiempirical methods. Many‐body electronic structure methods, almost routinely used for molecules, have been practically unavailable for sampling PES in the condensed‐phase. This has changed during the last few years, as efficient algorithms and software implementations for the evaluation of electronic energies and forces on atoms have been developed, allowing for geometry optimization, molecular dynamics and Monte‐Carlo simulations, which was previously unthinkable. Herein, we introduce the theory and software developments and overview the applications in the field, the most encouraging results being obtained for aqueous chemistry. Requiring state‐of‐the‐art computer resources PES sampling with many‐body electronic structure methods in the condensed phase provides high‐quality benchmarks and will gradually become more available due to fast progress in reduced scaling algorithms and computational technologies.