An interesting self-coupling/cyclization of 5-aminopyrazoles is revealed, which provides a variety of pyridazine cores in reasonable yields. In this reaction, C(sp2)-C(sp2) and N-N bond formation occurs simultaneously in one reaction vessel. The photophysical properties of the synthesized compounds were also studied and some of them exhibited fluorescence properties with good quantum yields. A radical mediated reaction mechanism is proposed with the help of control experiments.