Polyvinyl pyrrolidone (PVP) based titanium n-butoxide (TNBT) and zirconium n-propoxide (ZNP) composite fibres were prepared by electrospinning, and the corresponding fibres with the addition of acetic acid (HAc) were also prepared for comparison. The storage stabilities of four alkoxide composite fibres and PVP electrospun fibres under standard laboratory conditions (20 degrees C, 65% relative humidity) were investigated. Some unexpected but interesting phenomena were discovered. Electrospun PVP fibres lose their fibrous shapes after they have been stored for only 24 h. The TNBT, ZNP and ZNP(HAc) composite fibres still remain their morphologies even though they have been stored for 15 days, exhibiting excellent chemical and morphological stability in the air, because the hydrolysis and condensation of alkoxide have completed during the electrospinning process, while TBNT(HAc) composite fibres hydrolyse and condense during the storage period. This investigation provides useful knowledge for preparing ceramic electrospun fibres, especially for large scale production or electrospinning over extended time.