CaCu3Ti4O12 (CCTO) fibre, a new form of CCTO, is facilely fabricated in a batch size using standard electrospinning equipment. CCTO fibres with different morphological and chemical structures can be prepared by changing the composition of the precursor solution and the calcination temperature, and the pure phase CCTO fibres were successfully fabricated using suitable process parameters. Based on the successful preparation of CCTO fibres, a novel composite based on CCTO fibres and cyanate ester (CE) resin was prepared for measuring the dielectric constant of CCTO fibres. An interesting phenomenon is found that CCTO fibre has different dielectric constant from CCTO bulk ceramic, suggesting that the production of CCTO fibres not only provides a new and big chance for intensively investigating the origin of dielectric property for CCTO, but also supplies a great potential for developing new high performance composites. (C) 2012 Elsevier B.V. All rights reserved.