The structural defects including dislocations and grain boundaries (GBs) in upgraded metallurgical grade silicon (UMG-Si) prepared by vacuum directional solidification were investigated. The results demonstrated that higher withdrawal rates increased the dislocation density. The state of melt growth changed from quasi-equilibrium to non-equilibrium, and the GB type was also highly related to the withdrawal rate, especially for ∑3 boundary. The change of total interfacial energy and increase of carbon concentration may be a possible driving mechanism for this phenomenon.