Inexpensive fabrication of europium (Eu3+)-doped zinc oxide (ZnO) nanoparticles, nanorods, and urchin systems obtained by rapid thermal annealing is being reported. The polyvinyl alcohol films containing a reactant mixture [Zn(CH3COO)2, Eu(CH3COO)3, and NaOH] were casted on Al-foils followed by thermal annealing at 80, 300, and 650 °C. Gradual change-over from spherically symmetric nanoparticles to nanorods along with urchin like structures are obtained under different annealing environment. The nanorods and urchins are expected to have grown as a result of spontaneous decomposition of Zn(OH)2 followed by unidirectional growth. The nanorods are dislodged from the regular urchin structures at a high annealing temperature of 650 °C because of the loss of the crystalline substrate support. The as-received ZnO products possessed hexagonal wurtzite structure for all the annealing cases-as evident from the x-ray diffraction patterns. The photoluminescence study on the samples has revealed dominant defect related emissions compared to the near band edge emission. The band edge emission (∼382 nm) is recovered in the urchin systems whereas Eu3+ related transitions observed at ∼591 nm (5D0→7F1) and ∼613 nm (5D0→7F2) rema- - ined intact with structural modification.