This study focuses on the meaning of Duccio's certain early masterpiece begun in 1285, his Rucellai Madonna: its iconography, style, spatial structure and ornament, to serve as the basis of a more extended examination of his artistic career and sphere of influence, to be examined in a later publication. It also comments on its relationship to two works of art not far removed in time, the tiny Madonna of the Three Franciscans in the Siena Pinacoteca, and especially the round stained glass window from Siena Cathedral that has been attributed to both Duccio and Cimabue.