只要设置Picturebox的Region属性就可以了,如下
using System.Drawing.Drawing2D;
private void button1_Click(object sender, EventArgs e)
{
GraphicsPath gp = new GraphicsPath();
gp.AddEllipse(pictureBox1.ClientRectangle);
Region region = new Region(gp);
pictureBox1.Region = region;
gp.Dispose();
region.Dispose();
}