ZnO crystallites were grown by electroless deposition on poly(methyl methacrylate) (PMMA) fiber mats prepared by an electrospinning technique. The electroless deposition involves three steps: sensitization, activation and deposition, which were performed by subsequently dipping the PMMA fiber mats in the appropriate solutions. After the deposition the PMMA fibers are uniformly coated with ZnO prisms which show hexagonal wurtzite structure and optical signatures (band-gap value and emission bands) typical for this semiconductor. By combining electroless deposition and electrospinning, different semiconductor coated polymer fibers can be obtained for a wide range of applications. Both methods are appropriate for large scale production, being scalable, cheap, efficient and suitable for large-area covering techniques. •ZnO-coated PMMA fibers were prepared by combining two low cost and scalable techniques: electrospinning and electroless deposition.•PMMA fibers were uniformly coated with ZnO prisms shaped crystallites.•ZnO prisms show a hexagonal wurtzite structure and optical signatures typical for this semiconductor (band-gap value and emission bands).