1. Open Photoshop. Open the image to
create Two Colored frame.

2. Create New file with 640 X 480 Pixels and drag
the image on it using Move tool.
3. Create a new layer in the middle of background
and image layer. Keep it Selected. You can name it as a BASE frame
layer if you want.
4. Draw rectangular selection around the image for
frame using Rectangular Marquee Tool, on the BASE frame layer. View
> Show > Grid for the accuracy.
5. Fill rectangle with the desired color. Deselect
using CTRL + D.
6. Draw another rectangle using Rectangular Marquee
tool, inside the previous rectangle and delete the portion to get
following frame. Deselect using CTRL + D.

7. Create a new layer below the BASE frame layer.
Draw another rectangle using Rectangular Marquee tool, around the
image that will cover the white portion between the image and the
frame. Fill it with desired color. Deselect using CTRL + D.

8. Select the BASE frame layer.
9. Layer > Layer Style
> Bevel and Emboss (Style : Inner Bevel)
10. Image > Trim to trim the image.

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