MEGARA is an optical integral field and multi-object fibre-based spectrograph for the 10.4m Gran Telescopio CANARIAS that offers medium to high spectral resolutions (FWHM) of R ≃ 6000, 12000, 20000. Commissioned at the telescope in 2017, it started operation as a common-user instrument in 2018. We are creating an instrument-oriented empirical spectral library from MEGARA-GTC stars observations, MEGASTAR, crucial for the correct interpretation of MEGARA data. This piece of work describes the content of the first release of MEGASTAR, formed by the spectra of 414 stars observed with R ≃ 20000 in the spectral intervals 6420 – 6790 Å and 8370 – 8885 Å, and obtained with a continuum average signal to noise ratio around 260. We describe the release sample, the observations, the data reduction procedure and the MEGASTAR database. Additionally, we include in Appendix A, an atlas with the complete set of 838 spectra of this first release of the MEGASTAR catalogue.