In this work, electrospun zinc ferrite fibers with spinel structure were produced under different conditions and investigated in spinel|3M ZnSO4 + buffered aqueous electrolyte|Zn cells comparing acetate-based buffers at different pH levels with a commercially available phthalate and a homemade phthalate buffer, as well as an MES-based buffer. Previous work in our group showed that application of ZnFe₂O₄ in combination with aqueous electrolytes leads to irreproducible results. This can be overcome by using electrospun fibers with improved surface area in combination with a buffered aqueous electrolyte. In addition, it was demonstrated that the adequate buffer composition and pH allow for moderation of additional processes in the cell, especially proton co-insertion.