The purpose of this study is to prepare multifunctional polymer fibers. We report a simple and controllable method for in situ synthesis of Ag nanoclusters (NCs) in electrospun polymer fibers via a photochemical reaction. The prepared composite polymer fibers emit pink luminescence and the luminescence property can be optimized by pH and Ag(I) precursor concentration. The as-prepared Ag NCs in electrospun polymer fibers were mainly Ag2-5 with a quantum yield of 6.81% and a lifetime of 2.29 ns. The in situ growth of Ag NCs avoids excessive surface modifications which may cause the aggregation of Ag NCs in many ex situ assembly methods. The combination of Ag NCs with polymer fibers greatly improves the stability of Ag NCs and broadens their applications. The storage of Ag NCs becomes facilitative due to the formation of bulky mat. Furthermore, these luminescence composite polymer fibers show strong antibacterial activity against Staphylococcus aureus (S. aureus). (C) 2014 Elsevier B.V. All rights reserved.