We present a homogeneous set of stellar atmospheric parameters (Teff, logg, [Fe/H]) for MILES, a new spectral stellar library covering the range λλ 3525-7500Å at 2.3Å (FWHM) spectral resolution. The library consists of 985 stars spanning a large range in atmospheric parameters, from super-metal-rich, cool stars to hot, metal-poor stars. The spectral resolution, spectral type coverage and number of stars represent a substantial improvement over previous libraries used in population synthesis models. The atmospheric parameters that we present here are the result of a previous, extensive compilation from the literature. In order to construct a homogeneous data set of atmospheric parameters we have taken the sample of stars of Soubiran, Katz & Cayrel, which has very well determined fundamental parameters, as the standard reference system for our field stars, and have calibrated and bootstrapped the data from other papers against it. The atmospheric parameters for our cluster stars have also been revised and updated according to recent metallicity scales, colour-temperature relations and improved set of isochrones.