Both...
It was most likely done with PS in the first place, but then added to an image via a plugin -- like "Extensis PhotoFrames" or "AutoFX Photographic Edges". [honesty]
Those types of borders are really much more simple to create than people first imagine them to be. At least half of PS's native filter set can produce or help produce effects like that.
Here's some examples (i've outlined the inside ones so the edges are visible). These are all duplicates of the original layer.
-- On a New Layer, create a rectangle and fill it with black. Deselect.
-- Change the Foreground swatch to white. Then go to FILTER>Brush Strokes>Spatter : 25/8
To extend the effect, also apply FILTER>Artistic>Dry Brush : 0/10/3
To extend the effect still further, also apply FILTER>Pixelate>Crystalize : 13
And you can do this 'filter combining' method forever.
To breath more life into a filter's effect, apply the FILTER>Other>Maximum filter to the layer first. Use a setting of 2. When you do this, you'll see exactly what effect it has on the image. Example #2 was done like this. And should you need/want a specific edge effect, there's always the good ol' brushes and selection tools.
TIP: Most of the filters will add white to areas where the black has been altered. This means that although you're seeing a crooked black edge, there's a solid, straight white edge still in your image. This will prevent you from using your border effectively --
for clipping, masking, or overlaying.
The method to resolve this issue, and remove the white areas from your borer pattern, is to open the SELECT menu, choose "Color Range...", the change the Select option to "Highlights". Click OK, the press Delete. Then Deselect.
You'll then have only the black border you need to work with. But take note now before doing this part... once you remove the white areas, the filters will behave diferently then they did originally.
Experiment to get an understanding of how they react after doing this.
PS: These shapes would be put on a layer below your photo or other image.
PPS: The example you attached Lee has been blurred and/or smudged manually after it's basic outline was created.