The high-resolution carbon Is photoelectron spectrum of trans-1,3-pentadiene has been resolved into contributions from the five inequivalent carbon atoms, and carbon Is ionization energies have been assigned to each of these atoms. Spectra have also been measured for propene and 1,3-butadiene at better resolution than has previously been available. The ionization energies for the sp(2) carbons are found to correlate well with activation energies for electrophilic addition and with proton affinities. Comparing the results for 1,3-pentadiene with those for ethene, propene, and 1,3-butadiene as well as with results of theoretical calculations makes it is possible to assess the effect of the terminal methyl group in 1,3-pentadiene. As in propene, the methyl group contributes electrons to the carbon through the 7 system. In addition, there is a significant (though smaller) contribution from the methyl group to the terminal (delta) CH2 carbon, also through the T system. Most of the effect of the methyl group is present in the ground-state molecule. There are only relatively small contributions from the methyl group to the ionization energies from redistribution of charge in the 7 system in response to the removal of a core electron. In addition to these specific effects, there is an overall decrease in average ionization energy as the size of the molecule increases as well as effects that are specific to the conjugated systems in 1,3-butadiene and 1,3-pentadiene. The results provide insight into the reactivity and regioselectivity of conjugated dienes.