The presented work studies the processes of synthesis of nitrogen-containing structures of ZnO using atmospheric pressure microwave nitrogen plasma and investigates their photocatalytic activity in the processes of degradation of 2,4-dinitrophenol and the antibiotic ciprofloxacin when irradiated with sunlight. The work proposes an effective method for formation of photosensitive ZnO powders. Due to the features of plasma treatment in the open atmosphere of zinc metal microparticles, ZnO structures are formed with sizes from hundreds of nanometers to several micrometers with various micromorphologies. High photoactivity was demonstrated (rate constants 0.036 min-1 and 0.051 min-1) of synthesized ZnO structures during photo-degradation of 2,4-dinitrophenol and ciprofloxacin, respectively, when exposed to solar radiation. Photo-active structures of ZnO synthesized using microwave nitrogen plasma can find application in processes of mineralization of toxic organic compounds.