The C Is excitation spectra of propyne (HC2CH3) 3,3,3-trifluoropropyne (HC2CF3) and propargyl alcohol (HC2CH2OH) have been studied using synchrotron radiation and ion time-of-flight mass spectrometry. Discrete peaks below the carbon Is ionization thresholds are compared and assigned, aided in part by ab-initio calculations incorporating an explicit C 1s hole. Calculated C 1s ionization potentials are in good agreement with previously reported experimental values. Calculated absolute excitation energies consistently underestimate the transition term values, but calculated relative excitation energies and intensities are in good agreement with the experimental results. The spectra are dominated by intense C 1s -> pi* transitions. In the case of propyne, C 1s excitations from each of the three chemically inequivalent carbon atoms are observed. The effect of electronegative substitution is found to be different for the C 1s -> Rydberg transitions than for transitions to unoccupied valence levels, with Rydberg transition energies shifting with changes in the C Is ionization potentials but valence transition energies showing only small changes with electronegative substitution. The C 1s (3a(1),4a(1)) -> pi* (6e) transitions of trifluoropropyne are shifted to lower energy relative to propyne even though the electronegative fluorine atoms cause a significant shift to higher energy in the corresponding C 1s IPs.