AbstractIn this work, results are presented concerning solar spectral irradiance measurements performed in Madrid in the wavelength range 250–2500 nm, that is, extending the spectral range far away from the wavelengths where PV semiconductors are active. These data were obtained considering a horizontal receiver surface during selected clear days covering the four seasons of the year. PV materials having different spectral responses (m‐Si, a‐Si, CIGS, CdTe) have been considered to calculate spectral factors (SF) taking as reference the standard solar spectrum AM1.5 defined in standard IEC 60904‐3. From these SFs, the influence of natural solar spectral variations in PV conversion has been established. It is shown, for example, that PV technologies based on a‐Si are highly favored, from the spectral point of view, in spring–summer compared to other technologies having broader spectral responses, which are more favored in autumn–winter. From the experimental measured solar spectra, we have calculated Weighed Solar Spectra (WSS) corresponding to the four seasons of the year and also to the whole year. The WSS represents, for a certain period of time, the solar spectrum weighed over the irradiance level. SFs have been calculated for different WSSs showing spectral gains for the four PV materials during almost the full year. Otherwise, it is also shown in this work how the near‐IR part of the solar spectrum affects the evaluation of the solar resource as a whole when reference solar cells made of different PV materials are used. For typical m‐Si, a‐Si, CIGS, and CdTe solar cells, the ratio of Isc over global irradiance is not constant along a given day showing variations that depend on the season and on the PV material considered. © 2006 John Wiley & Sons, Ltd.