根据属性去改
属性–ColumnHeadersDefaultCellStyle–Alignment–MiddleCenter
dataGridView1.ColumnHeadersDefaultCellStyle.Alignment = DataGridViewContentAlignment.MiddleCenter;
属性–Columns–DefaultCellStyle–Alignment–MiddleRight
dataGridView1.DefaultCellStyle.Alignment = DataGridViewContentAlignment.MiddleCenter;