Emission spectra of intra- and intermolecular exciplex systems of benzophenone and MA-dimethylaniline were studied in detail at low temperature. Two new emissions were observed for the first time in the present work in addition to the well-known phosphorescence of the CT complex formed in the ground state. The first emission has a lifetime of a few tens nanoseconds, which is common to intra- and intermolecular systems. The second emission with a longer lifetime than that of the first one is obtained only in the case of the intramolecular system. A possibility that these emissions are due to fluorescent products was examined. Considering solvent, temperature, and concentration dependences of these emissions, it is proposed that the first and the second emissions are due to the singlet and the triplet exciplexes, respectively. Dynamic behaviors and geometrical structures of these exciplexes are discussed.