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MEGARA is the optical integral field and multi-object spectrograph at the Gran Telescopio Canarias. We have created MEGASTAR, an empirical library of stellar spectra obtained using MEGARA at high resolution $R=20\,000$ (FWHM), available in two wavelength ranges: one centered in H$α$, from 6420 to 6790\,Å and the other centered in the \ion{Ca}{ii} triplet, from 8370 to 8885\,Å (\mbox{HR-R} and \mbox{HR-I} VPH-grating configurations). In this work, we use MEGASTAR spectra, combination of these two short wavelength intervals, to estimate the stellar parameters namely effective temperature, surface gravity and metallicity (and their associated errors) for a sample of 351 MEGASTAR members with spectral types earlier than B2. We have applied a $χ^2$ technique by comparing MEGASTAR data to theoretical stellar models. For those stars with stellar parameters derived in the literature, we have obtained a good agreement between those published parameters and ours. Besides the stellar parameters, we also provide several products like the rectified spectra, radial velocities and stellar indices for this sample of stars. In a near future, we will use MEGASTAR spectra and their derived stellar parameters to compute stellar population evolutionary synthesis models, which will contribute to a better interpretation of star clusters and galaxies spectra obtained with MEGARA.