The interactions of cesium cations with five amino acids (AA) including glycine (Gly), proline (Pro), serine (Ser), threonine (Thr), and cysteine (Cys) are examined in detail. Experimentally, the bond dissociation energies (BDEs) are determined using threshold collision-induced dissociation of the Cs+(AA) complexes with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Bond dissociation energies (0 K) of 93.3 +/- 2.5, 107.9 +/- 4.6, 102.3 +/- 4.1, 105.4 +/- 4.3, and 96.8 +/- 4.2 kJ/mol are determined for complexes of Cs+ with Gly, Pro, Ser, Thr, and Cys, respectively. Quantum chemical calculations are conducted at the B3LYP, B3P86, MP2(full), and M06 levels of theory with geometries and zero-point energies calculated at the B3LYP level using both HW*/6-311+G(2d,2p) and def2-TZVPPD basis sets. Results obtained using the former basis sets are systematically low compared to the experimental bond energies, whereas the latter basis sets show good agreement. For Cs+(Gly), theory predicts the ground-state conformer has the cesium cation binding to the carbonyl group of the carboxylic acid. For Cs+(Pro), the secondary nitrogen accepts the carboxylic acid hydrogen to form the zwitterionic structure, and the metal cation binds to both oxygens. Cs+(Ser), Cs+(Thr), and Cs+(Cys) are found to have tridentate binding at the MP2(full) level, whereas the density functional approaches slightly prefer bidentate binding of Cs+ at the carboxylic acid moiety. Comparison of these results to those for the smaller alkali cations provides insight into the trends in binding affinities and structures associated with metal cation variations.