The ZrBi composite materials were prepared in a single step by the chemical coprecipitation method. Bi2O2(CO3) joined ZrxOy modifying the mole percentage from 5 to 11 mole ZrBi composites dried at 80 ° C were characterized by: XRD, FTIR, DRS, SEM, N2 adsorption, HR-TEM, PL, XPS and EDS-SEM. Later they were evaluated in the photodegradation of 4-Chlorophenol under UV irradiation. The degradation and mineralization percentages were determined after 150 minutes of reaction by UV-Vis spectroscopy and Total Organic Carbon (TOC), respectively. The composite containing 9 mol% of Bi2O2(CO3) (ZrBi-9) showed the highest photoactivity with 96% photodegradation. Finally, a possible reaction mechanism was proposed based on recent studies, which allow to follow the formation of active species •OH, •O2- and h+. The results showed that ZrBi composite materials do not promote •OH radical formation. The scavenge of h+ showed a total loss of photoactivity and the inhibition of •O2- in the reaction medium results in a partial decrease of photoactivityThe formation of heterojunctions, the presence of localized states and oxygen vacancies in the synthesized materials promise an excellent alternative for the rapid photodegradation of 4-Chlorophenol under UV radiation.