Hybrid organic-inorganic materials are a new class of materials used as interfacial layers (ILs) in polymer solar cells (PSCs). A hybrid material, composed of antimony as the inorganic part and diaminopyridine as the organic part, is synthesized and described as a new material for application as the electron extraction layer (EEL) in PSCs and compared to the recently demonstrated hybrid materials using bismuth instead of antimony. The hybrid compound is solution-processed onto the photoactive layer based on a classical blend, which is composed of a PTB7-Th low band gap polymer as the donor mixed with PC70BM fullerene as the acceptor material. By using a regular device structure and an aluminum cathode, the solar cells exhibited a power conversion efficiency of 8.42%, equivalent to the reference device using ZnO nanocrystals as the IL, and strongly improved compared to the bismuth-based hybrid material. The processing of extraction layers up to a thickness of 80 nm of such hybrid material reveals that the change from bismuth to antimony has strongly improved the charge extraction and transport properties of the hybrid materials. Interestingly, nanocomposites made of the hybrid material mixed with ZnO nanocrystals in a 1:1 ratio further improved the electronic properties of the extraction layers, leading to a power conversion efficiency of 9.74%. This was addressed to a more closely packed morphology of the hybrid layer, leading to further improved electron extraction. It is important to note that these hybrid EELs, both pure and ZnO-doped, also greatly improved the stability of solar cells, both under dark storage in air and under lighting under an inert atmosphere compared to solar cells treated with ZnO intermediate layers.