We report detailed prompt emission observations and analysis of the very bright and long GRB 210619B, detected by the Atmosphere-Space Interactions Monitor (ASIM) installed on the International Space Station (ISS) and the Gamma-ray Burst Monitor (GBM) on-board the Fermi mission. Our main goal is to understand the radiation mechanisms and jet composition of GRB 210619B. With a measured redshift of 𝑧 = 1.937 we find that GRB 210619B falls within the 10 most luminous bursts observed by Fermi so far. The energy-resolved prompt emission light curve of GRB 210619B exhibits an extremely bright hard emission pulse followed by softer/longer emission pulses. The low-energy photon indices (𝛼 pt ) values obtained using the time-resolved spectral analysis of the burst reveal a transition between the thermal (during harder pulse) to non-thermal (during softer pulse) outflow. We examine the correlation between spectral parameters and find that both peak energy and 𝛼 pt exhibit the flux tracking pattern. The late time broadband photometric dataset can be explained within the framework of the external forward shock model with 𝜈 𝑚 < 𝜈 𝑐 < 𝜈 𝑥 (where 𝜈 𝑚 , 𝜈 𝑐 , and 𝜈 𝑥 are the synchrotron peak, cooling-break, and X-ray frequencies, respectively) spectral regime supporting a rarely observed hard electron energy index (𝑝 < 2). We find moderate values of host extinction of E(B-V) = 0.14 ± 0.01 for the Small Magellanic Cloud (SMC) extinction law. In addition, we also report late-time optical observations with the 10.4 m GTC placing deep upper limits for the host galaxy (located at 𝑧=1.937), favouring a faint, dwarf host for the burst.