Thomson scattering measurements are presented which demonstrate conclusively the occurrence of the Langmuir decay instability (LDI) in a laser-produced plasma experiment. Both products of the instability, the ion acoustic wave and the electron plasma wave, were simultaneously observed and identified with their spectral characteristics. The secondary decay of the LDI-generated electron plasma wave, into another Langmuir wave and an ion acoustic wave, has been observed for the first time. The connection with growth and saturation of the stimulated Raman instability is discussed.