The synthesis of Bi2O2(CO3)/Zn5(CO3)2(OH)6 heterojunction at low-temperature and template-free synthesis was carried out promoting the growth of sheet-like structures. The novel material has shown a high photocatalytic performance in the phenol removal under UV light when is compared to the Zn5(CO3)2(OH)6 and Bi2O2(CO3) bare photocatalysts. It is worth mentioning that, the material composed by a molar ratio of Bi/Zn = 0.08 showed the highest percentage of phenol mineralization. All the synthesized materials were characterized by X-ray diffraction, infrared spectroscopy with Fourier transform, diffuse reflectance spectroscopy, adsorption-desorption isotherms of N2, X-ray photoelectron spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. The addition of Bi2O2(CO3) to the Zn5(CO3)2(OH)6 structure promotes the oxygen vacancies (OV) increment which make slower the recombination process between the e− and h+ species. This is because the OV sites act like a trap of the photogenerated holes. Thus, the photocatalytic activity is enhanced when Zn5(CO3)2(OH)6 is modified by the addition of Bi2O2(CO3) propitiate an increase on the production of hydroxyl and superoxide radicals as oxidant species for the phenol removal. As a novel material, Bi2O2(CO3)/Zn5(CO3)2(OH)6 could potentially be applied as an efficient material for phenol removal in photocatalysis due to the high performance, facile preparation and the synergetic effect achieved by the heterojunction presence.