Context. The X-shooter Spectral Library (XSL) is a large empirical stellar library used as a benchmark for the development of stellar population models. The inclusion of α-element abundances is crucial to disentangling the chemical evolution of any stellar system. Aims. The aim of this paper is to provide a catalogue of high-precision, accurate magnesium and calcium abundances from a wide variety of stars that are well distributed in the Hertzsprung-Russell (HR) diagram. Methods. We originally performed an analysis of the derived Mg and Ca abundances for medium-resolution spectra of 611 stars from the XSL Data Release 2. For this purpose, we used the GAUGUIN automated abundance estimation code to fit the ultravioletblue (UVB) and visible (VIS) spectra. We tested the consistency of the atmospheric parameters and chemical abundances with the Gaia DR3 and the AMBRE Project datasets. Results. We finally obtained precise [Mg/Fe] and [Ca/Fe] abundances for 192 and 217 stars, respectively, from which 174 stars have measurements in both elements. The stars cover a broad effective temperature range of 4000 < T eff < 6500 K, surface gravity of 0.3 < log(g) < 4.8 cm s −2 , and metallicity of -2.5 < [Fe/H] < +0.4 dex. We find an excellent agreement with the abundance estimates from the AMBRE:HARPS and the Gaia-RVS (Radial Velocity Spectrometer) analysis. Moreover, the resulting abundances reproduce a plateau in the metal-poor regime followed by a decreasing trend even at supersolar metallicities, as predicted by Galactic chemical evolution models. Conclusions. This catalogue is suitable for improving the modelling of evolutionary stellar population models with empirical α enhancements, which could significantly contribute to the analysis of external galaxies' abundances in the near future.