To date, small molecule-based organic solar cells (SMOSCs) using p-type small molecules and n-type fullerenes have achieved remarkable PCEs by using either solution-processed or vacuum-deposited fabrication techniques. The search for new donor materials with promising physical properties has taken the center stage. Along this line, a large number of donor molecules with interesting molecular architectures have been extensively investigated to perform varying degrees of success. We recently reported new organic molecules adopting a donor-acceptor-acceptor (D-A-A) configuration, in which an electron-donating moiety is connected to an electron-withdrawing dicyanovinylene moiety through another electron-accepting arene, exhibited narrow optical band gaps and lower HOMO levels, showing potential to concurrently enhance the short circuit current density (Jsc) and open circuit voltage (Voc) as employed in organic photovoltaics. In this symposium, vacuum-processed devices incorporating D-A-A type donors and fullerene (C70) acceptor achieved power conversion efficiencies exceeding 9% will be reported.