A novel donor-acceptor molecular system with a beta-diketone bridge, 1-(4-cyanophenyl)-3-(4-(N,N-dimethylamino)phenyl)-1,3-propanedione (DMA >$($) over bar CB) was synthesized and investigated in tuning of emission by metal cation coordination. From the solvent polarity dependence of Stokes shift, it was revealed that the excited state has a considerable charge-transfer (CT) character. The time-resolved fluorescence study in the picosecond region indicates that the photophysical behavior can be interpreted with the typical two-state model (LE and TICT states) similar to the normal TICT compounds. Complexation of DMA >$($) over bar CB with Mg2+ resulted in a blue-shift of the emission maxima and a change of emission intensity, whose ratio was sensitively dependent on the solvent polarity. The nonradiative decay rate constants (k(nr)) of DMA >$($) over bar CB and its Mg2+ complex (DMA(Mg)CB) increased exponentially with decreasing of the emission energy maxima (E(em)). However the slopes of the in k(nr)-E(em) plots were quite different in each case. From this relation it becomes obvious that the dominant vibrational accepting mode to k(rn) is affected by the structural restriction around the beta-diketone moiety by the Mg2+ coordination. This indicates the probability of controlling the emission properties from TICT excited state with metal cation coordination.