In this work, we investigate blade-coated organic interlayers at the rear surface of hybrid organic-silicon photovoltaics based on two small molecules: Tris(8-hydroxyquinolinato) aluminium (Alq3) and 1,3-bis(2-(4- Tert-butylphenyl)-1,3,4-oxadiazol-5-yl) benzene (OXD-7). In particular, soluble Alq3 resulting in a uniform thin film with a root-mean-square roughness < 0.2nm is demonstrated for the first time. Both devices with the Alq3 and OXD-7 interlayers show notable enhancement in the open-circuit voltage and fill-factor, leading to a net efficiency increase by over 2% from the reference, up to 11.8% and 12.5% respectively. The capacitance-voltage characteristics confirm the role of the small-molecule interlayers resembling a thin interfacial oxide layer for the Al-Si Schottky barrier to enhance the built-in potential and facilitate charge transport. Moreover, the Alq3 interlayer in optimized devices exhibits isolated phases with a large surface roughness, in contrast to the OXD-7 which forms a continuous uniform thin film. The distinct morphological differences between the two interlayers further suggest different enhancement mechanisms and hence offer versatile functionalities to the advent of hybrid organic-silicon photovoltaics.