Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics. As one possible nucleosynthesis scenario, break-out from the hot carbon–nitrogen–oxygen (HCNO) cycle was thought to be the source of the calcium observed in these oldest stars. However, according to the stellar modeling, a nearly tenfold increase in the thermonuclear rate ratio of the break-out \(^{19}\) F(p, \(\gamma\) ) \(^{20}\) Ne reaction with respect to the competing \(^{19}\) F(p, \(\alpha\) ) \(^{16}\) O back-processing reaction is required to reproduce the observed calcium abundance. We performed a direct measurement of this break-out reaction at the China Jinping underground laboratory. The measurement was performed down to the low-energy limit of \(E_\mathrm {c.m.}\) = 186 keV in the center-of-mass frame. The key resonance was observed at 225.2 keV for the first time. At a temperature of approximately 0.1 GK, this new resonance enhanced the thermonuclear \(^{19}\) F(p, \(\gamma\) ) \(^{20}\) Ne rate by up to a factor of \(\approx\) 7.4, compared with the previously recommended NACRE rate. This is of particular interest to the study of the evolution of the first stars and implies a stronger breakdown in their “warm” CNO cycle through the \(^{19}\) F(p, \(\gamma\) ) \(^{20}\) Ne reaction than previously envisioned. This break-out resulted in the production of the calcium observed in the oldest stars, enhancing our understanding of the evolution of the first stars.