Calculations are reported on the structure, transition energies, and ground and excited state dipole moments of substituted N,N-dimethylanilines using both the AM1 method and a version of the CNDO/S method. The former gives a reasonable structural correlation with crystallographic data for N,N-dimethyl-4-nitroaniline and with data calculated at the ab initio level using a 3-21G basis set, but the excited state properties are unsatisfactory despite the use of a multielectron configuration interaction treatment. The CNDO method appears to give a much better correlation with the experimental data, and both the transition energies and the large change in the magnitude of the dipole moments produced on excitation for these molecules are well reproduced.