Physical alginate hydrogels commonly rely on "internal gelation" to introduce the cross-linker, e.g., calcium (Ca(II)) ions. These are released in a homogeneous manner by using a pH-sensitive Ca(II) carrier and glucono-delta-lactone (GDL) as the acidifier. Yet, it remains unclear how the carrier of the cross-linker affects the gelation process and final hydrogel properties. We therefore investigate two internal gelation methods using either Ca(II)-chelating ligand complexes or insoluble Ca(II)-based salts. Ionometry coupled with pH measurements reveals the release process of Ca(II) ions upon acidification, which is well described by simulations using the Hyperquad Simulation and Speciation program. We show that these findings correlate well with the evolution of the mechanical properties of the hydrogels. Although the two pH-triggered gelation methods appear to be similar, we demonstrate their differences in terms of the gelation kinetics and final cross-link density. The nature of the ligand or the salt significantly affects the fraction of the released Ca(II) ions and, hence, the mechanical properties of the final hydrogel for a given GDL concentration. Furthermore, for the first time, we demonstrate the competition between GDL and alginate in binding with Ca(II) ions. This study therefore provides different tools for the efficient formulation of alginate hydrogels.