Espero que este codigo te sirva
Point tmp;
private void pictureBox1_MouseMove(object sender, System.Windows.Forms.MouseEventArgs a){
if (e.Button == System.Windows.Forms.MouseButtons.Left)
if(tmp==null)
tmp = new Point(e.X, e.Y);
else
g.DrawLine(System.Drawing.Pens.Black,tmp,new Point(e.X,e.Y));
else
tmp=null;
}