Innovative technologies based on the sulfate radical advanced oxidation process are attracting more attention for the degradation of dyes in impure water. Herein, cobalt‐doped zinc aluminum layered double hydroxide (LDH) catalysts are synthesized based on the assembly of LDHs for efficient activation of peroxymonosulfate and simultaneous catalytic degradation of rhodamine B (RhB) and methyl orange (MO). Cobalt metal is incorporated into the ZnAl‐LDH lattice to accelerate the catalytic performance of ZnAl‐LDHs. The experimental results show that the Co–ZnAl‐LDH (Co = 0.05 mmol) system demonstrates remarkable degradation of RhB and MO with maximum degradation efficiencies of 98.97% and 98.04%, respectively, through the attack of reactive oxygen species and electron transfer processes. Furthermore, the structural stability and catalytic performance of the catalyst make it promising for practical water treatment as well as promoting its reuse ability.