The elastic moduli of individual electrospun polyethylene oxide fibres were measured using atomic force microscopy based indentation. Heating of the fibres below their melting temperature produced a considerable degradation in mechanical behaviour associated with a loss in the original electrospun polymer structural organization. Indentation of fibres at just below their melting temperature followed by cooling to room temperature resulted in characteristic stepped morphology at the indentation point. This solid state ordering of the polymer at the indentation point showed an improved elastic modulus as compared with the post-thermal treatment behaviour of the fibre away from the indentation point.