Alginate-based hydrogels are promising smart materials widely employed in the food, bioengineering, and energy sectors. The development and optimization of their production require a thorough knowledge of gelation. In recent years, advanced experimental procedures have been developed for real-time cross-linking alginate reaction monitoring. Novel methods, such as customized rheometric setups, enable the recording of mechanical properties and morphological changes during hydrogel formation. These innovative techniques provide important insights into the gelation stages, the reaction rate, the diffusion of cross-linker to polymer chains, and the homogeneity of the gelling structures. Based on real-time experimental data, kinetic models are developed to enhance comprehension of the reaction mechanism and, eventually, to predict the gelation progress. The aim is to enable better control of the characterization of both the complex gelation and the propagated structures. This review aspires to present a comprehensive overview and evaluation of the breakthrough innovations of the real-time in situ recording of cross-linking alginate hydrogels and bead formation. A detailed analysis of the pioneering experimental developments provides a deep comprehension of the alginate gelation, including the parameters controlling the reaction.