Electrospinning has emerged as an attractive technique for the fabrication of ultrafine fibres in micro-/nano-scale fineness: however, it remains a significant technological challenge to assemble aligned fibre arrays via an conventional electrospinning method due to the inherent whipping instability of the polymeric jet. We herein have first developed a simple modified electrospinning method with which to prepare ultralong (>300 mm) well-aligned inorganic fibre arrays, i.e., using an ultrahigh molecular weight polymer to suppress or eliminate the whipping motion of the electrospun jet, has emerged as a facile approach for the continuous fabrication of well-aligned, ultralong fibres through simply using a rotating cylinder as the collector (it was not found necessary to use a very high rotating speed, extra magnetic, electrical field) in the electrospinning process. As result, the ultralong well-aligned TiO2:Ln3+ (Ln = Eu, Sm, or Er) fibre arrays can be obtained from ultrahigh molecular weight poly(ethylene oxide), tetra-n-butyl titanate (Ti(OC4H9)4) and lanthanide nitrate in the modified electrospinning approach. The grow mechanism and luminescent properties of these ultralong well-aligned TiO2:Ln3+ fibre arrays were also investigated.