In this paper we report a simple and effective approach towards improving the performance of molecular bulk heterojunction (BHJ) photovoltaics through incorporation of a new, nonvolatile processing additive; (3-chloropropyl) trimethoxysilane (CP3MS). A small amount of the additive CP3MS combined with post-annealing treatment significantly enhanced the power conversion efficiency (PCE) of dialkylated diketopyrrolopyrrole chromophore (SMDPPEH)-based molecular BHJ solar cells. The PCE increased from 2.75% for a device prepared without the additive or annealing to 4.55% for a device containing 0.1% CP3MS that had been subjected to post-annealing treatment at 100 °C for 10 min. CP3MS performed an interesting dual function when incorporated as an additive in molecular BHJ devices. The first was that it controlled the morphology: the addition of 0.1% CP3MS to the SMDPPEH:PC 61 BM blend was sufficient to improve the film's crystallinity and morphology. The second function was the spontaneous migration of the CP3MS molecules from the bulk to the interface between the active layer and the Al cathode, forming an ultrathin interlayer that acted as a buffer layer suppressing charge recombination and enhancing charge transport at the interface. Analyses using atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, together with examinations of device performance, confirmed the dual-functional nature of CP3MS as an additive. CP3MS also showed its promising ability to enhance the performance of different blend systems. The performance of benzodithiophene (BDT)-based molecular solar cells enhanced from 3.05% without additive to 3.8% with the incorporation of 0.1% CP3MS.