The characterization of acido-basic properties of the surface of inorganic solids is essential to understand the behavior of catalysts during heterogeneous catalyzed reactions. The use of alcohols as reactive probe molecules to investigate these properties has been developed since the 1970s, and in 1991, a new alcohol, 2-methylbut-3-yn-2-ol (MBOH), was proposed. This review sums up the knowledge accumulated for 15 years on this model reaction network and compares its advantages with those of other alcohols. The operating conditions are reviewed, and deactivation phenomena are analyzed. Then, from investigations of correlations with other techniques able to reveal the acido-basic properties of surfaces, it is concluded that MBOH appears to be the most valuable reactive probe molecule as the nature of the sites involved in the different routes of its network is unambiguous. The links that may exist between the rate of a model reaction and the thermodynamic acido-basic properties of the surface are then discussed. It is shown that even when true kinetics parameters are available, they are not necessarily correlated to thermodynamic parameters. What can be expected from a model reaction network is to evaluate the reactivity of a surface along an acidic or a basic route. In basic sites, this reactivity may be related to the nucleophilicity of the surface or to the way the deprotonated intermediate is stabilized on the surface. It can be used to follow the modifications of a series of materials during synthesis and to identify the factors governing a reaction of practical interest.