Semiconductor photocatalysis with the Z‐scheme mechanism is regarded as a promising approach in enhancing photocatalytic performance. A novel Z‐scheme I‐BiOBr/C3N4 heterostructure is successfully synthesized via a hydrothermal method. The as‐prepared catalyst exhibits superior photocatalytic degradation performance of various organic pollutants (tetracycline, rhodamine, and norfloxacin). Meanwhile, the optimized catalyst shows an enhanced photocatalytic hydrogen evolution rate in contrast to pristine BiOBr, I‐BiOBr, and g‐C3N4. The enhanced photocatalytic performance is ascribed to the widened visible light absorption range and efficient carriers’ transportation. The Z‐scheme mechanism is based on X‐ray photoelectron spectroscopy, active radical capture experiments, and electron spin resonance spectroscopy. This research work provides an angle of view on designing other Z‐scheme photocatalytic materials.