We have obtained [Mg/Fe] for around 77% of the stars of the MILES library of stellar spectra in order to include this important information into simple stellar population (SSP) models. The abundance ratios, which were carefully calibrated to a single uniform scale, were obtained through a compilation from high spectral resolution works plus robust spectroscopic analysis at medium resolution. The high resolution data provided an extensive control sample. Average uncertainties (0.06 and 0.12 dex for the high and medium resolution samples respectively) and the good coverage of the stars with [Mg/Fe] over the MILES's parameter space will permit us to semi-empirically build up new SSP models with accurate α-enhancements for ages older than 1 Gyr. This will open new prospects for evolutionary stellar population synthesis.