13C and some selected 1H NMR chemical shifts of conjugated (E)-enynes of the type of (E)-2-alken-4-yn-1-ols (RC≡CCH=CHCH2OH; R = H, Me, Et, n-Pr, n-Bu, SiMe3), (E)-2-alken-4-yn-1-yl acetates (RC≡CCH=CHCH2OAc; R = H, Me, Et, n-Pr, n-Bu) and (E)-2-alken-4-yn-1-als (RC≡CCH=CHCH=O; R = Et, n-Pr) and of (2Z,4E)-deca-2,4-dien-6-yne as a conjugated (Z,E)-dienyne were measured. The unequivocal assignment of the 13C NMR chemical shifts is based on the application of standard techniques such as H,H-COSY, C,H-COSY and APT and, above all, on the investigation of the C,C connectivities by determination of the one-bond 13C,13C coupling constants 1JC,C. These coupling constants show typical values for the different structural fragments. The effect of increments of the alkyl group on the resonances of the acetylenic carbon atoms are compared with those of the n-alkynes. The shift effects observed on going from (E)-2-alken-4-yn-1-ols to (E)-2-alken-4-yn-1-als are discussed in comparison with results from other classes of compounds. © 1997 John Wiley & Sons, Ltd.