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In the present study, intriguing nanocolumnar-shaped Mn-doped ZnO (Mn:ZnO) films have been prepared by a simple and scalable two-step chemical bath deposition technique. Firstly, the ZnO nano-seeds were deposited on a glass substrate, and in the second step, the hexagonal pyramidal-shaped Mn:ZnO arrays were grown regularly as well as vertically based on the ZnO seeds. The optical properties of the nanocolumnar-shaped Mn:ZnO films have been investigated in detail. Interestingly, the reflectance measurements demonstrate that the nanocolumnar-shaped Mn:ZnO films are an excellent candidate for antireflection coatings, showing a significantly low reflectance over the entire visible spectrum. The inverse hexagonal pyramidal-shaped Mn:ZnO films with antireflection and photon-trapping properties have great potential for their integration into nanoscale devices, especially thin-film solar cells.