The present review discusses the current state of the art microscopic and spectroscopic characterization techniques available to study surfaces and interfaces under working conditions. Microscopic techniques such as environmental transmission electron microscopy and in situ transmission electron microscopy are first discussed showing their applications in the field of nanomaterials and catalysis. Next sum frequency generation vibrational spectroscopy is discussed, giving probing examples of surface studies in gaseous conditions. Synchrotron based X‐ray techniques are also examined with a specific focus on ambient pressure X‐ray photoelectron and absorption techniques such as near and extended X‐ray absorption fine structure. Each of the techniques is evaluated, whilst the pros and cons are discussed in term of surface sensitivity, spatial resolution and/or time resolution. The second part of the articles is articulated around the future of in situ characterization, giving examples of the probable development of the discussed techniques as well as an introduction of emerging tools such as scanning transmission X‐ray microscopy, ptychography, and X‐ray photon correlation spectroscopy.