Electrohydrodynamic jetting has been widely used as a promising strategy for the development of functionalized scaffolds to mimic natural extracellular matrix. The current electrospun scaffolds achieve functionality through additional mechanical or chemical treatments, and their lifetime depends on fiber degradation. An innovative in situ approach used to attach core-shell poly(D, L-lactide-co-glycolide) (PLGA) particles on fibrous mats is described here. This particle/fiber composite was prepared by electrohydrodynamic jetting of countercharged nozzles (EJC) based on neutralization between electrospun nanofibers and coaxial electrosprayed droplets. The PLGA particles were successfully attached onto both water-soluble polyvinylpyrrolidone and hydrophobic poly(L-lactide-co-D, L-lactide). The resulting release rates of encapsulated model compounds were independently controlled by fiber degradation. Encapsulation efficiency and the dimensions of particles and fibers were easily engineered by changing solvents. The particle/fiber composite prepared by EJC could be a superior material for developing future biomaterials with architectured biological and mechanical properties.