Synthesis of metal molybdates (XMoO₄, X = Ca, Sr, Ba) have received much attention recently because of their interesting structural and luminescent properties. Here novel erythrocyte-like CaMoO₄ hierarchical nanostructures are synthesized via a simple surfactant-free hydrothermal route. The formation of the calcium molybdate erythrocytes is controllable through adjusting the fundamental experimental parameters including reaction time, temperature and DMAc to H₂O ratio. The as-synthesized products are characterized using X-ray powder diffraction, scanning electron microscopy, Brunauer–Emmett–Teller and transmission electron microscopy. The results show that the nucleation and growth of the novel erythrocyte-like CaMoO₄ hierarchical nanostructures are governed by an oriented attachment growth mechanism. The luminescent properties of the CaMoO₄ erythrocytes are then studied using a spectrophotometer and the erythrocyte-like CaMoO₄ nanostructures display a strong blue emission. This study provides an easy surfactant-free synthetic route for the controllable construction of inorganic materials with high hierarchy in the absence of any surfactants.