Probably not on its own, but as a composting material it can be used. Remember that creating your own fertilizer requires much more biomass then will be produced. So, coffee grounds with your orange peel and the bad bread will work. A truck full of coffee grounds, not as well. Building and using a composting bin will help a lot. Building it far from any windows that may be open in the summer heat will help even more.
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Used coffee grounds are excellent in compost, or scattered wet or dry over lawns and under shrubs. Earth worms like used coffee grounds, and their travel to reach the snack will also naturally loosen and aerate compacted soils. Earthworms also help fertilize the yard and garden, as their droppings are left behind.
Gardeners can visit Coffee Shops to ask for bags or bins of used coffee grounds one or more times a year. Be sure to re-use the bags also. Starbucks sometimes offers used grounds in shiny foil bags - but since these are manufacturing intensive, ask if they have a large bag ready to go instead of the expensive foil bags...or bring in your own 5 gal bucket with lid for their collected grounds to be dumped into. Ice cream stores will sell or give these to you, and they have many uses in the garden.
Perhaps in very small quantities - a quarter of a teaspoonful would not harm anybody. But there is no good reason to include used coffee grounds in food. However, they do make a nice addition to garden mulch.
Of course you can. It might do a little damage to your stomach, if you know what I mean.. ;)