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Abstract Emission lines from Rydberg transitions are detected for the first time from a region close to the surface of Betelgeuse. The H30αline is observed at 231.905 GHz, with an FWHM ∼42 km s⁻¹and extended wings. A second line at 232.025 GHz (FWHM ∼21 km s⁻¹), is modeled as a combination of Rydberg transitions of abundant low first ionization potential metals. Both H30αand the Rydberg combined line X30αare fitted by Voigt profiles, and collisional broadening with electrons may be partly responsible for the Lorentzian contribution, indicating electron densities of a few 10⁸cm⁻³. X30αis located in a relatively smooth ring at a projected radius of 0.9× the optical photospheric radiusR_⋆, whereas H30αis more clumpy, reaching a peak at ∼1.4R_⋆. We use a semiempirical thermodynamic atmospheric model of Betelgeuse to compute the 232 GHz (1.29 mm) continuum and line profiles making simple assumptions. Photoionized abundant metals dominate the electron density, and the predicted surface of continuum optical depth unity at 232 GHz occurs at ∼1.3R_⋆, in good agreement with observations. Assuming a Saha–Boltzmann distribution for the level populations of Mg, Si, and Fe, the model predicts that the X30αemission arises in a region of radially increasing temperature and turbulence. Inclusion of ionized C and non-LTE effects could modify the integrated fluxes and location of emission. These simulations confirm the identity of the Rydberg transition lines observed toward Betelgeuse and reveal that such diagnostics can improve future atmospheric models.