Sure - use the pen tool, or even easier - use a font that has a heart for a symbol, raster the layer, select the heart with the magic wand, press delete to remove the fill, then stroke the selection as desired.
In the tools pallet the "Vector Shape Tools" include the rectangle tool, ellipse tool, line tool and the "Custom Shape Tool"...choose the custom shape tool.
There should appear a drop down list box with shape selections where you can choose the Heart.
There is also another icon that lets you control the way the shape is drawn like from inside out, custom defined size, or no control, etc.
Now click on your layer and while holding down the left mouse move your mouse to see the heart appear and keep moving the mouse out until the desired size is optained.
if you hold the Ctrl key or shift key (i forget which one) while drawing the shape maintains it's original proportions.
now you can follow dmacster's method fopr selecting and removing all but the outline.
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