You can add picture into the picture box using 2 methods.
1. When you are making the project. Picture will get inserted into the binary.
You can add image location by selecting properties of picturebox and providing path to ImageLocation property.
2. You can add picture dynamically, that is during run time. In this case picture is not inside binary, it is present at some location in the hard disk.
You can update ImageLocation property during runtime as shown below.
public Form1()
{
InitializeComponent();
pictureBox2.ImageLocation = @"E:\TP\Songs\AlbumArtSmall.jpg";
}