In this paper, a novel kind of Poly(butylene succinate) (PBSU) /wollastonite/apatite composite scaffold was fabricated via electrospinning and biomimetic process. Pure PBSU scaffold and composite scaffolds with 12.5 wt% and 25 wt% wollastonite were firstly fabricated by electrospinning. SEM micrographs showed that all the electrospun scaffolds had homogeneous fibrous structures with interconnected pores and randomly oriented ultrafine fibers. The composite scaffolds were then surface modified using a biomimetic process. SEM and XRD results showed that apatite could deposit on the surfaces of the composite fibers after incubation in SBF and a novel fibrous structure with microspheres composed of worm-like apatite on composite fibers was formed. Incubation time and wollastonite content were found to influence the morphology of the scaffolds during the biomimetic process obviously. Both the amount and the size of the microspheres on the composite scaffolds increased with increased incubation time. After a certain incubation time, microspheres formed on the composite fibers with less wollastonite had a relatively larger size. Therefore, the microstructure of the composite scaffolds could be adjusted by controlling the wollastonite content and the incubation time. All of these results suggest that it is an effective approach to fabricate PBSU/wollastonite/apatite fibrous composite scaffolds with different material content and controllable microstructure for bone tissue engineering.