Electrospun polymeric scaffolds are used for various tissue engineering applications. In this study, we applied a biomimetic coating method to provide electrospun scaffolds from a block copolymer-poly(ethylene oxide terephthalate)−poly(buthylene terephthalate), with a calcium phosphate layer to improve their bioactivity in bone tissue engineering. The in vitro studies with human mesenchymal stem cells demonstrated cell proliferation on both uncoated and coated samples. No significant effect of calcium phosphate coating was observed on the expression of alkaline phosphatase in vitro. Implantation of scaffold−goat mesenchymal stem cells constructs subcutaneously in nude mice resulted in bone formation in the calcium phosphate coated samples, in contrast to the uncoated ones, where no new bone formation was observed. The results of this study showed that the biomimetic method can successfully be used to coat electrospun scaffolds with a calcium phosphate layer, which improved the in vivo bioactivity of the polymer.