AbstractThe13C and19F (when appropriate) chemical shifts of a variety of di‐, tri‐ and tetrasubstituted methanes of the type CH2XCOOEt (I), CHXYCOOEt (II) and CXYZCOOEt (III), where the substituents X, Y and Z are F, Br, OEt, OPh, SEt, SPh and NO2, were determined. The prediction of the observed C‐α chemical shifts of I, II and III based on the simple additivity of substituent effects in monosubstituted methanes [MeX; SCS(IV)] is not satisfactory, although those of I are well correlated with SCS (IV). The C‐α chemical shifts of II and III can be correlated in terms of the multi‐parameter analysis of individual SCS (I), the difference between δ (CH2XCOOEt) and δ (CH3COOEt). The origin of the chemical shifts is discussed. The19F chemical shifts of I, II and III were also satisfactorily analysed in terms