Time variation of microwave dielectric absorption has been examined for photolyzed aniline (ANI) and N,N-dimethylaniline (DMA) in CCl4 solvent and their solutions admired with CCl4 in benzene solvent. In CCl4 solvent, the signals for both ANI and DMA show formation of highly polar transients, which are attributed to contact ion pairs (CIP) : ANI(+)Cl(-) for ANI and possibly (DMA)(2)Cl-+(-) for DMA. In benzene solvent, both ANI and DMA form the CIPs not via excited triplet states but by direct excitation of a preexisting complex, ANI . CCl4 and DMA . CCl4. In ANI the CIPs subsequently decay by back electron transfer, deprotonation with simultaneous recombination with H+, or a reaction with another CCl4 molecule, leading to HCl and other less-polar products, while in DMA the CIPs further react with a CCl4 molecule to produce even polar species. A few experiments show that the mechanism of CIP formation (and decay) for N-methylaniline is similar to that for ANI. The quantum yields for the CIP formation may be equal to or lower than 0.5 for both ANI and DMA.