This work presents the evaluation by empirically derived equations for the substituent effect (α, β, γ, δ) on the13C NMR chemical shifts for C-1, C-2, C-3 and C-4 in β-alcoxyvinylhalomethylketones 1a–h to 3a–h [R3C(O)-C(R2)=C(R1-OR, where R1= H, alkyl or phenyl, R2= H, alkyl or hetero-alkyl, and R3= di- or trihalomethyl], taking as reference the compound la. From the calculated values for the α, β, γ, δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1–3. The13C chemical shifts of the C-1, C-2, C-3, C-4 of these compounds, can be estimated with good to rasoable precision: 93% of the calculated chemical shifts are found to be within ±2.0ppm, and 100% are found to be within ±3.0ppm.