On the basis of 1,2,3-triols 1a approximately d, 1,2,3,4-tetraols 2a approximately h, and 1,2,3,4,5-pentaols 3a approximately p, NMR databases with four types of profile-descriptors ((13)C-, (1)H-, and (1)H(OH)-chemical shifts and vicinal spin-coupling constants) for contiguous polyols are reported. To systematically assess the relative values of these databases, a case study has been conducted on heptaols 4a approximately d, through which the gamma- and delta-effects have been recognized to refine the (13)C and (1)H chemical shift profile predicted via an application of the concept of self-contained nature. The magnitudes of gamma- and delta-effects depend on a specific stereochemical arrangement of the functional groups present in both the inside and outside of a self-contained box and are significant only for the stereoisomers belonging to a specific sub-group. With the exception of the stereochemical arrangement of functional groups belonging to a specific sub-group, the gamma- and delta-effects can, at the first order of approximation, be ignored for the stereochemical analysis of unknown compounds. For the stereoisomers belonging to a specific sub-group, it is necessary to refine, with incorporation of the gamma- and delta-effects, the profile predicted at the first order of approximation. With use of heptaols 4a approximately d, the values of (3)J(H,H) profiles have been assessed. Two methods, one using profiles consisting of three contiguous (3)J(H,H) constants and the other using profiles consisting of two contiguous (3)J(H,H) constants, have been developed. A stereochemical analysis based on three, or two, contiguous (3)J(H,H) profiles is operationally simpler than one based on (13)C and (1)H chemical shift profiles. Therefore, it is recommended to use a (3)J(H,H) profile as the primary device to predict the stereochemistry of unknown polyols and (13)C and (1)H chemical shift profiles as the secondary devices to confirm the predicted stereochemistry.