I know this is old, but for those surfing this question, the answer by MUG4N will align all columns that use the same defaultcellstyle. I'm not using autogeneratecolumns so that is not acceptable. Instead I used:
e.Column.DefaultCellStyle = new DataGridViewCellStyle(e.Column.DefaultCellStyle);
e.Column.DefaultCellStyle.Alignment = DataGridViewContentAlignment.MiddleRight;
While we are dealing with alignment and configuration it can be useful to reduce repetitive tasks by using (C#) anonymous types. Much easier to read and advanced operations can be edited in one place. Like in this datagridview dg configuration
foreach (var conf in new [] {
new { Col = 0, WidthPercent = 40, Align = DataGridViewContentAlignment.MiddleCenter } ,
new { Col = 1, WidthPercent = 30, Align = DataGridViewContentAlignment.MiddleCenter } ,
new { Col = 2, WidthPercent = 30, Align = DataGridViewContentAlignment.MiddleCenter }
})
{
dg.Columns[conf.Col].Width = (int)(dg.Width * conf.WidthPercent/100);
dg.Columns[conf.Col].DefaultCellStyle.Alignment = conf.Align;
}