The adsorption process of a geminized amphiphilic polyelectrolyte, comprising double elementary charges and double hydrophobic tails in each repeat unit (denoted as PAGC(8)), was investigated and characterized by means of quartz crystal microbalance with dissipation (QCM-D), ellipsometry, and atomic force microscopy (AFM). By comparison, the self-assembly behaviors of a traditional polyelectrolyte without hydrophobic chains (denoted as PASC(1)) and an amphiphilic polyelectrolyte with a single hydrophilic headgroup and hydrophobic tail in each repeat unit (denoted as PASC(8)) at the solid/liquid interface were also investigated in parallel. A two-regime buildup was found in both amphiphilic systems of PASC(8) and PAGC(8), where the first regime was dependent on electrostatic interactions between polyelectrolytes and oppositely charged substrates, and the rearrangements of the preadsorbed chains and their aggregation behaviors on surface dominated the second regime. Furthermore, it was found that the adsorbed amount and conformation changed as a function of the charge density and bulk concentrations of the polyelectrolytes. The comparison of the adsorbed mass obtained from QCM-D and ellipsometry allowed calculating the coupling water content which reached high values and indicated a flexible aggregate conformation in the presence of PAGC(8), resulting in controlling the suspension stability even at an extremely low concentration. In order to provide an insight into the mechanism of the suspension stability of colloidal dispersions, we gave a further explanation with respect to the interactions between surfaces in the presence of the geminized polyelectrolyte.