We report a novel approach to control the defect-mediated visible photoluminescence (PL) of small ZnO nanoparticles (NPs) by changing the ionic environment viz. concentration of LiClO4 or NaCl (electrolytes) in the medium in which NPs are dispersed. For both the electrolytes,
overall intensity of visible PL emission decreases and the spectral components (∼2.35 eV and ∼2.19 eV) of it shift towards lower energy side with increase in electrolyte concentration. Such changes are more prominent in case of NaCl than LiClO4. We have explained all these
observations in the basis of accumulation of surface charge, due to the presence of electrolyte, which controls the band bending in the depletion layer at the surface of the NPs. Furthermore, the band bending results in corresponding change of number of emission centres (here, relative number
of singly ionized oxygen vacancies or doubly ionized oxygen vacancies) which predominantly decides the nature of visible emission. An enhancement of this effect has been observed in case of smaller NPs of size comparable to the width of the depletion layer. This study can open up a way to
control the visible emission from the ZnO NPs and can be useful for sensing the processes involving surface charge in the fields such as biophysics and biochemistry.