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A self-assembling chemical route assisted by complexing agent has been designed to control the synthesis of semiconductor YF3 nanospindles, in which it has been demonstrated that complex geometrical objects of micro- and nanoscales can be prepared by a simple and template-free solution route. The X-ray powder diffraction, transmission electron microscopy, field emission scanning electron microscopy and high-resolution transmission electron microscopy examinations show that the authors' strategy is reasonable and successful. Different structured YF3 nanospindles composed of uniform nanoparticles, nanoplates and nanowires with a mean thick size of 30 nm have been prepared through controlling reaction time and temperatures. Two new emission peaks at 415 and 433 nm owing to SeO42 ions were observed as excited by 370 nm.