Background: The purpose of this study was to elucidate the association between sentinel lymph node (SLN) metastasis and Ki67 labeling index and to elucidate whether Ki-67 was useful or not for prediction of SLN metastasis in breast cancer. Methods: We identified 343 invasive breast cancer patients with sentinel lymph node biopsy (SLNB) from 2003 to 2012. The association between SLN status and clinicopathological features, molecular subtypes and Ki-67 labeling index were evaluated. Results: SLN metastasis was detected in 79 patients (23.0%). SLN metastasis was significantly associated with clinical T-stage (p = 0.0003), lymphovascular involvement (LVI) (p < 0.0001). Ki-67 labeling index of primary tumor was significantly lower in SLN positive patients (p = 0.0331), and Ki-67 cut-off point of 7.5% was useful for dividing SLN positive from negative (p = 0.0197). Conclusion: Low value of Ki-67 labeling index, in addition to progression of clinical T-stage and presence of LVI, is significantly associated with SLN metastasis, and it seems to be useful to consider Ki-67 labeling index for SLN metastasis prediction.