The results of recent measurements by energy dispersive X-ray fluorescence and IR reflectography of Raffaello's picture Marriage of the Virgin (Brera, Milano) are given. AM*h241*s and Cd*h109*s XRF exciting sources and Ge(I) detector, liquid nitrogen cooled, were used. Seventy spots (0 ~ 8mm) in different colour zones were examined. Medium/high atomic number elements (Zgreater than20) were detected and corresponding pigments identified, as azurite, copper green, ochre, cinnabar, umber, lead white. Ultramarine blue and red lake were identified indirectly. The underdrawing was investigated using IR reflectography. Hamamatzu camera and Vidicon N 214.06, with 1.2mu cut on filter, were employed. The results are in general quite satisfactory, especially for architectural details and for the Virgin's dress draperies.