This is how I go about it.
Using the rounded rectangle tool, draw a rectangle from the top left corner to the bottom right corner. Adjust the radius and redo as needed.
Next, CTRL+Click on the layer with the rounded rectangle to select it.
CTRL+SHIFT+I to invert the selection
Create a new layer and fill it with your background color (white?)
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to add a border, so that it truly looks like a rounded frame:
Switch your background color to the color you used for the fill above.
Edit>Canvas Size
expand the canvas size, according to the size of the image. (800x600...850x650, 6"x4"...6.25"x4.25") the size is all a matter of personal taste, and the effect that you want to acheive from your frame.
Done.
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