Iterative multiple linear regression analysis of substituent-induced chemical shifts in 3- and 4-substituted styrene derivatives is used to redefine σF and [Formula: see text] substituent constants (with respective standard errors of ca. 0.01 and 0.005). Correlations with the data for various model systems indicate that these substituent constants are applicable to data sets involving both chemical shift and acidity measurements in aprotic media. The approach we have used involving a homogeneous data set with a large number of variables is particularly suited for providing well-defined dual substituent parameter constants for the more common neutral substituents.Correlations for individual nuclei are entirely consistent with a previously proposed model of substituent effects involving field, resonance, and polarization effects. From these results and the results for other model systems, it is concluded that σF and [Formula: see text] are respectively pure field and resonance substituent constants. It is pointed out that a combination of detailed statistical testing and chemical modelling is essential for a thorough understanding of aromatic substituent effects.Parameters for predicting non-electronic contributions to ortho and meta chemical shifts are derived, thus allowing the patterns of electronic substituent effects for these carbons to be determined. However, only an approximate ipso factor can be deduced.