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Select a picture which you want to situate into the photo frame. Create a new layer, fill it with the white color and put it to the background.
Create a square vector object in front of the main object. This should be the OUTER border of your frame.
The square should have white color.
On this tutorial image, I set 50% visibility to that square, so you can see what's the main object.

Duplicate square layer and pull the size down with Free transform (T) togeather with holding Shift and Alt keys (you will constrain Proportions with this).
In my tutorial, I have used the RED color for displaying this square (You can use any colors).
It's better again to pull visibility down to see what area is filled with this square.

On the layers bar, find an icon for creating "Layer Mask" (In my image, green rectangle). When you will click on it, layer mask for the original image will be aplied in 100% white (that means 100% of visibility).
In the next step, press and hold Ctrl key and klick to the shape (inner border of photoframe) layer (in my image, blue arrow).
You will get inner border selected on the image layer mask.
Then press Ctrl+Shift+I (Menu "Select->Inverse") for inverting the selection.

with the Bucket tool (B) you will fill the layer mask with solid 100% BLACK color (pay attention for Opacity settings for this tool (it should be on 100%).

With the Pen tool (P), make the "shadow path" around the image (inner border).
Don't forget to do the path below to the outer border (as the shadow should be below everything).
If you want and know how to, you can make curved paths for more realistic effect. Pen tool in my tutorial has gray color of foreground #929292 or you can use the color from the image (the gray smudge on the left side).

(183 days ago)