Electrospinning nanotechnology has recently attracted lots of attention in different kinds of applications. Poly(butylene terephthalate) random-segment copolymers, named poly[(butylene terephthalate)-co-(1,4-cyclohexanedimethanol terephthalate)]-b-poly(tetramethylene glycol) (P(BT- co-CT)-b-PTMG), were synthesized in this study. On the basis of the new thermoplastic polyester elastomers (TPEEs), the fiber membranes were subsequently electrospun. With the aid of a cosolvent of trifluoroacetic acid and dichloromethane, the resulting solutions with a concentration between 24 and 32% w/v were electrospun into fibers without beads. The results also show a good spinnability for the copolymer solution in a range of voltages from 16 to 24 kV. When the molar ratio of 1,4-cyclohexanedimethanol to 1,4-butanediol was 10 : 90, the electrospun membrane prepared by the corresponding copolymers had a higher elastic modulus than the commercial TPEE (Hytrel 4056, 4.51 +/- 6 0.35 MPa). Differential scanning calorimetry and X-ray diffraction showed that a crystalline phase existed in the electrospun poly[(butylene terephthalate)-co-(1,4-cyclohexanedimethanol terephthalate)]-b-poly(tetramethylene glycol) (P(BT-co-CT)-b-PTMG) copolymer fiber membranes. The melting point of the electrospun fibers was approximately less than that of the corresponding copolymers (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 1698-1706, 2011