This work reports on the shape‐controlled synthesis of CaMoO4 nanorods via a high‐efficient microwave irradiation‐assisted chelating agent method. The phase and microstructure of these materials were systematically characterized by X‐ray diffraction and field‐emission scanning electron microscopy. It is noteworthy that EDTA plays pivotal roles as the complexing and capping agent in the oriented growth of uniform CaMoO4 nanorods. The synthetic process gives the guidance to understand the morphological evolution of CaMoO4 microstructures in microwave system, and provides a facile and designed strategy to fabricate functional one dimensional metallic molybdates.