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Electrical conductimetry and dynamic light scattering (DLS) were used to investigate the aggregation behaviors of four amino acid-based surfactants (AABSs; undecanoyl-glycine, undecanoyl-l-alanine, undecanoyl-l-valine, undecanoyl-l-leucine) in the presence of five linear diamine counterions (1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane). Electrical conductimetry was used to measure the CMCs for each system, which ranged from 5.1 to 22.5 mM. With respect to counterions, the obtained CMCs decreased with increases in the interamine spacer length; this was attributed to the improved torsional binding flexibility in longer counterions. Strong linear correlations (mean R2 = 0.9443) were observed between the CMCs and predicted surfactant partition coefficients (logP; water/octanol), suggesting that micellization is primarily driven by the AABS’s hydrophobicity for these systems. However, significant deviations in this linear relationship were observed for systems containing 1,2-diaminoethane, 1,4-diaminobutane, and 1,6-diaminohexane (p = 0.0774), suggesting altered binding dynamics for these counterions. pH measurements during the CMC determination experiments indicated the full deprotonation of the AABSs but did not give clear insights into the counterion protonation states, thus yielding an inconclusive evaluation of their charge stabilization effects during binding. However, DLS measurements revealed that the micellar size remained largely independent of the counterion length for counterions longer than 1,2-diaminoethane, with hydrodynamic diameters ranging from 2.2 to 2.8 nm. This was explained by the formation of charge-stabilized noncovalent dimers, with each counterion bearing a full +2 charge. Conductimetry-based estimates of the degrees of counterion binding (β) and free energies of micellization (ΔG°M) revealed that bulky AABSs exhibit preferential binding to counterions with an even number of methylene groups. It is proposed that when these counterions form noncovalent dimers, perturbations in their natural geometries result in the formation of a binding pocket that accommodates the AABS steric bulk. While the direct application of these systems remains to be seen, this study provides valuable insights into the structure–property relationships that govern AABS aggregation.