Electrospinning was used to prepare PLA-PCL-diOH copolymer (PCLA) nanofibers with different alignments via adjusting the shape of collector. In order to lay the foundation of choosing proper aligned fibers in various applied fields, studying the parameters of collector was important. When the two collectors were parallel, the aligned degree of the fibers was decreased with the increased distance between the collectors. However, when the distance was 3 cm, the highest aligned degree occurred. This was due to the different electrostatic field force caused by the distance and the different length of ejected fibers. When the included angle of the two collectors was 60o, the aligned degree of the fibers was obviously higher than the one obtained by parallel method. This indicated that adjusting the included angle of collectors was helpful to improve the alignment of fibers. When the collector was latticed, the obtained fibers exhibited structure of cross and parallel. When the collector was hollowed out with a hexagon, the fibers were overlapped with a 3- dimensional structure. All in all, the aligned degree was decided on the shape of collectors. The research was meaningful for the fields which needed directional fibers such as cell culture, polarizing film and so on.