Poly(ester amide)s (PEAs) are lacking in structural and spectroscopic information. This paper reports a structural and spectroscopic characterization of N(α)-benzoyl-L-argininate ethyl ester chloride (BAEEH(+)·Cl(-)), an important amino acid derivative and an adequate PEAs' model compound. Crystals of BAEEH(+)·Cl(-) obtained by slow evaporation in an ethanol∕water mixture were studied by different complementary techniques. X-ray analysis shows that BAEEH(+)·Cl(-) crystallizes in the chiral space group P2(1). There are two symmetry independent cations (and anions) in the unit cell. The two cations have different conformations: in one of them, the angle between the least-squares planes of the phenyl ring and the guanidyl group is 5.1(2)°, and in the other the corresponding angle is 13.3(2)°. There is an extensive network of H-bonds that assembles the ions in layers parallel to the ab plane. Experimental FT-IR and Raman spectra of BAEEH(+)·Cl(-) were recorded at room temperature in the 3750-600 cm(-1) and 3380-100 cm(-1) regions, respectively, and fully assigned. Both structural and spectroscopic analysis were supported by quantum chemistry calculations based on different models (in vacuo and solid-state DFT simulations).