Objective To observe the levels of serum VEGF in different molecular subtypes of breast cancer and explore its relationship with response to neoadjuvant chemotherapy. Methods Levels of serum VEGF in 110 cases with breast cancer underwent neoadjuvant chemotherapy were detected by ELISA prior to and after 3 cycles of neoadjuvant chemotherapy. Clinical response to neoadjuvant chemotherapy was evaluated by physical examination and ultrasonography. Results Levels of serum VEGF were significantly increased in breast cancer patients with≥4 lymph node metastasis than those with < 4 lymph node[(307.31 ± 101.42) pg/mL vs. (170.16 ± 73.07) pg/mL,P = 0.017]. Patients with positive HER-2 status had significantly higher levels of serum VEGF than those with HER-2 negative status [(235.15 ± 88.42 ) pg/mL vs. (179.82 ± 69.90) pg/mL, P = 0.024]. No significant difference was observed among age , menopausal status and hormone status. In patients with neoadjuvant chemotherapy of cCR and Cpr,the mean levels of serum VEGF were (205.75 ± 78.12) pg/mL and (226.04 ± 89.04) pg/mL, respectively. After 3 cycles of chemotherapy, levels of serum VEGF decreased to (145.15 ± 67.08) pg/mL and (161.27 ± 93.57) pg/mL. There was significant difference between two groups (P=0.009,0.014). In patients with SD or PD response, no significant difference was observed between levels of serum VEGF before and after chemotherapy (P = 0.577). Conclusions Levels of serum VEGF in breast cancer correlate with lymph nodes metastasis and HER-2 status and may decrease after neoadjuvant chemotherapy. However,whether or not the levels of serum VEGF can be used as a biomarker for response to neoadjuvant chemotherapy needs more further studies.