Iron oxyhydroxide [FeO(OH)] is a promising photocatalyst owing to its simple synthesis at mild temperatures and narrow band gap, which allows for the efficient harvesting of visible light. The selective production of FeO(OH) polymorphs and the modulation of their morphology by changing the iron salts, salt concentration, and additives have been widely reported. This study focuses on overcoming fast charge-carrier recombination by developing FeO(OH)-based heterostructure materials. The role of a chelating ligand (EDTA and citrate) in determining the polymorph type, morphology, and photocatalytic activity of FeO(OH) was studied. The findings revealed the additive produced of nanosized α-FeO(OH)/EDTA and layered γ-FeO(OH)/citrate with superior catalytic activities.