It is challenging to explore and prepare polyoxometalates-based nanomaterials (PNMs) with controllable morphologies and diversiform components. Herein, 3d-4f metals are introduced into isopolyoxometalates and Anderson-type polyoxometalates, CeCdW12 nanoflower and EuCrMo6 microflaky have been fabricated respectively. A series of control experiments are carried out to identify the impact factors on the rare morphologies in PNMs. Furthermore, upon excitation at 396 nm, the emission spectrum of EuCrMo6 displays five prominent f - f emitting peaks at 674, 685, 690, 707, and 734 nm that are assigned to Eu3+ 5D0 → 7FJ (J = 0, 1, 2, 3, 4) transitions. Meanwhile, the VSM results show that the Cr+3 ions in EuCrMo6 display anti-ferromagnetic interactions when the temperature is lower than - 17.54 K. After rising temperature, this material exhibits paramagnetic property. This work opens up strategies toward the brand new morphologies and components of PNMs, endowing this kind of material with new functions.