Canvas Size Method

Go to Image, then select "Canvas Size" which will open the Canvas Size Window
Here we have selected the Canvas extension colour, which will form the border, to be black, and set the sizes at 1cm width and 1cm height. You can choose the units of measurement, for example you might just want a key line of 2 pixels around the image. Keep the "Relative" box ticked so you can input the exact amount of the border you require.

Click OK and it's done. Remember that you can add multiple borders like this, using the same method for each successive border. You may for example want a small white line around the bordered image. Simply add a (for example) 4 pixel white border, followed by another 2 cm black border to give this effect.
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