The excited state behavior of the six m,n-dicyano-N,N-dimethylanilines (mnDCDMA) and m,n-dicyano-(N-methyl-N-isopropyl)-anilines (mnDCMIA) is discussed as a function of solvent polarity and temperature. The dicyano moiety in these electron donor (D)/acceptor (A) molecules has a considerably larger electron affinity than the benzonitrile subgroup in 4-(dimethylamino)benzonitrile (DMABN). Nevertheless, the fluorescence spectra of the mnDCDMAs and mnDCMIAs in n-hexane all consist of a single emission originating from the locally excited (LE) state, indicating that a reaction from LE to an intramolecular charge transfer (ICT) state does not take place. The calculated energies E(ICT), obtained by employing the reduction potential of the dicyanobenzene subgroups and the oxidation potential of the amino substituents trimethylamine (N(Me)(3)) and isopropyldimethylamine (iPrNMe(2)), are lower than E(LE). The absence of an LE -> ICT reaction threfore makes clear that the D and A units in the dicyanoanilines are not electronically decoupled. In the polar solvent acetonitrile (MOON), dual (LE + ICT) fluorescence is found with 24DCDMA and 34DCDMA, as well as with 24DCMIA, 25DCMIA, and 34DCMIA. For all other mnDCDMAs and mnDCMIAs, only LE emission is observed in MeCN. The ICT/LE fluorescence quantum yield ratio Phi'(ICT)/Phi(LE) in MeCN at 25 C is larger for 24DCDMA (1.2) than for 34DCDMA (0.35). The replacement of methyl by isopropyl in the amino substituent leads to a considerable increase of Phi'/(ICT)/Phi(LE), 8.8 for 24DCMIA and 1.4. for 34DCMIA, showing that the LE reversible arrow ICT equilibrium has shifted further toward ICT. The appearance of an ICT reaction with the 2,4- and 3,4-dicyanoanilines is caused by a relatively small energy gap Delta E(S(1),S(2)) between the two lowest excited singlet states as compared with the other m,n-dicyanoanilines, in accordance with the PICT model. The observation that the ICT reaction is more efficient for 24DCMIA and 34DCMIA than for their mnDCDMA counterparts is mainly caused by the fact that iPrNMe2 is a better election donor than N(Me)(3): E(D/D(+)) = 0.84 against 1.05 V vs SCE. That ICT also occurs with 25DCMIA, notwithstanding its large Delta E(S(1),S(2)), is due to the substantial amino twist angle theta = 42.6 degrees, which leads to partial electronic decoupling of the D and A subgroups. The dipole moments mu(c)(ICT) range between 18 D for 34DCMIA and 12 D for 25DCMIA, larger than the corresponding ye(LE) of 16 and 11 D. The difference between mu(e)(ICT) and mu(e)(LE) is smaller than with DMABN (17 and 10 D) because of noncollinear arrangement of the amino and cyano substituents (different dipole moment directions). The dicyanoanilines that undergo ICT have LE dipole moments between 9 and 16 D. From plots of Ine(Phi'(ICT)/Phi(LE)) vs 1000/T, the (rather-small) ICT reaction enthalpies Delta H could be measured in MeCN: 5.4 kJ/mol (24DCDMA), 4.7 kJ/mol (24DCMIA), and 3.9 kJ/mol (34DCMIA). With the mnDCDMAs and mnDCMIAs only showing LE emission, the fluorescence decays are single exponential, Whereas for those undergoing an LE -> ICT reaction the LE and ICT picosecond fluorescence decays are double exponential. In MeCN at 25 degrees C, the decay times tau(2) have values between 1.8 ps for 24DCMIA and 4.6 ps for 34DCMIA at 25 degrees C. Longer times are observed at lower temperatures. Arrhenius plots of the forward and backward ICT rate constants k(a) and k(d) of 25DCMIA in tetrahydrofuran, obtained from the LE and ICT fluorescence decays, give the activation energies E(a) = 4.5 kJ/mol and E(d) = 11.9 kJ/mol, i.e., Delta H = -7.4 kJ/mol. From femtosecond transient absorption spectra of 24DCDMA and 34DCDMA at 22 degrees C, ICT reaction times tau(2)= 1/(k(a) + k(d)) of 1.8 and 3.1 Ps are determined. By combining these results with the data for the fluorescence decays and Phi'(ICT)/Phi(LE), the values k(a) = 0. X 10(10) s(-1) (24DCDMA) and k(a) = 23 x 10(10) s(-1) (34DCDMA) are calculated. An LE and ICT excited state absorption is present even at a pump/probe delay time of 100 ps, showing that an LE reversible arrow ICT equilibrium is established.