Two sounds at exactly the same pitch. The foundation of any harmony — the root.
Unison is widely used in music for melody doubling (two instruments playing the same part), for rhythmic emphasis (repeating one note), and as a pedal tone in accompaniment. In rock and metal, unison bends create a characteristic "crying" effect.
Try finding the same note on two adjacent guitar strings and playing them simultaneously. This will help train your ear for perfect pitch matching. Practice unison bends: fret a note on one string, then bend the adjacent string up until it matches.
Learn to recognize intervals by ear with the interactive trainer.