Poly(l-lactic acid-co-ε-caprolactone) (P(LLA-CL)) is a kind of copolymer polymerized from lactic acid and ε-caprolactone. Electrospun P(LLA-CL) nanofibers have good biocompatibility, biodegradability, and mechanical property. However, this type of nanofibers will produce acid groups during the degradation, so that, the pH value of the environment will decrease and result in tissue inflammation. On the other hand, Magnesium (Mg) alloy tissue engineering scaffolds will show alkaline during the degradation because of the electrochemical corrosion. Based on the principle of acid-based neutralization, combination of these two kinds of materials through electrospinning could keep the pH of the degradation environment neutral. In this paper, fabrication and characterization of Mg/P(LLA-CL)-blended nanofiber scaffolds with different ratios will be studied by scanning electron microscopy and universal materials testing machines to observe the morphology and mechanical properties of nanofibers, respectively. Furthermore, PIECs were cultured and seeded on the scaffolds for different time to evaluate the proliferation behavior on the scaffolds by MTT assay. The degradation tests of the samples lasted for three months in phosphate-buffered saline to evaluate the pH values of degradation solutions and the weight loss of nanofibers during degradation. The results showed that the mechanical property and biocompatibility of Mg/P(LLA-CL)-blended nanofibers were worse than that of pure P(LLA-CL). Moreover, the addition of Mg in the nanofibers accelerated the weight loss of the Mg/P(LLA-CL) blending fibers and increased the pH values of the environment during degradation of Mg/P(LLA-CL)-blended nanofibers.