In the present work, polyvinyl alcohol (PVA) based Cadmium oxide (CdO) beads free nanofibers were success-fully deposited through an electrospinning method on a glass substrate fixed over an aluminium collector. The deposited PVA/CdO nanofibers were vacuum annealed followed by calcinated to yield one-dimensional CdO nano-grains. The calcined CdO was tested for various vapours and found better response towards formaldehyde vapour at elevated temperatures. Compositional, morphology and sensing mechanism were analysed and reported.