The structures of cycloalkanone-based threo and erythro aldols were investigated by systematic introduction of stereo-determining factors. The combination of single-crystal X-ray analysis and cryoscopic measurement and solution NMR and IR studies elucidated the detailed geometry of these typical aldols. Currently, X-ray diffraction is the only reliable spectroscopic method to determine the relative configuration of aldol,, Empirical NAM analysis can be safely applied in only limited cases. In hydrocarbon solvents, many aldols exist as monomers with an intramolecular OH . . .O=C hydrogen bond, but some compounds are in an equilibrium with higher aggregates via intermolecular hydrogen bonds. The aldols take various staggered conformers, where the relative stabilities are controlled largely by torsional strain affected by the size and nature of substituents. The intramolecular and intermolecular hydrogen bonds, gauche interactions between the vicinal. substituents, and sometimes CH/pi attractions significantly influence the distribution of conformers. The preferred structure in solution often differs greatly from the crystalline-state geometry.