Structural rearrangement in a latex powder during dry sintering at temperatures higher than the minimum film formation temperature was investigated by means of synchrotron small-angle X-ray scattering. Two major effects were identified: (1) Deformation of latex particles leads to a closure of voids between them and an extensive perfectioning of the face centered cubic colloidal crystalline ordering. Such an improvement of the colloidal crystalline structure involves preferential crystal growth along certain crystallographic directions as was evidenced by the measured unmatched relative diffraction intensity distribution of the crystallographic (111) and (220) planes. (2) Interdiffusion of polymeric chains between adjacent particles promotes a nanometer sized aggregation of nonpolymeric materials previously located in the interstices between particles. Size and size distribution of the aggregates at different dry sintering conditions were evaluated by using a model considering spheres dispersed in the system.