Abstract 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° bending. The flexible ceramic yarn may have potential application in functional textiles.