Nowadays, different kinds of polymers, including ceramics, are electrospun into fibrous materials with different structures by electrospinning. Generally, the as-spun ceramic fibers are randomly oriented membranes and brittle without flexibility. Here, we report the fabrication of flexible SiO2 electrospun yarns using poly (vinyl alcohol) (PVA) as a template through a conjugate electrospinning process and calcination. It was found that the calcined as-spun fibers and yarns are obviously thinned with PVA component removal. Fourier transform infrared spectroscopy and energy-dispersive spectroscopy examinations suggested that the obtained yarn after calcination was SiO2 yarn. The SiO2 yarn showed good flexibility without cracking after 180 degrees bending. The flexible ceramic yarn may have potential application in functional textiles.