We show that a precise control of deposition speed during the fabrication of polyfullerenes and donor polymer films by convective self-assembly leads to an optimized film microstructure comprised of interconnected crystalline polymer domains comparable to molecular dimensions intercalated with similar polyfullerene domains. Moreover, in blended films, we have found a correlation between deposition speed, the resulting microstructure, and photoluminescence quenching. The latter appeared more intense for lower deposition speeds due to a more favorable structuring at the nanoscale of the two donor and acceptor systems in the resulting blend films.