The ejecta composition is an open question in gamma-ray bursts (GRB) physics 1 . Some GRBs possess a quasi-thermal spectral component in the time-resolved spectral analysis 2 , suggesting a hot fireball origin. Others show a featureless non-thermal spectrum known as the "Band" function 3-5 , consistent with a synchrotron radiation origin 5,6 and suggesting that the jet is Poynting-flux-dominated at the central engine and likely in the emission region as well 7,8 . There are also bursts showing a subdominant thermal component and a dominant synchrotron component 9 , suggesting a likely hybrid jet composition 10 . Here we report an extraordinarily bright GRB 160625B, simultaneously observed in gamma-rays and optical wavelengths, whose prompt emission consists of three isolated episodes separated by long quiescent intervals, with the durations of each "sub-burst" being ∼ 0.8 s, 35 s, and 212 s, respectively. Its high brightness (with isotropic peak luminosity L p,iso ∼ 4 × 10 53 erg/s) allows us to conduct detailed time-resolved spectral analysis in each episode, from precursor to main burst and to extended emission. The spectral properties of the first two sub-bursts are distinctly different, allowing us to observe the transition from thermal to non-thermal radiation between well-separated emission episodes within a single GRB. Such a transition is a clear indication of the change of jet composition from a fireball to a Poynting-flux-dominated jet.