Born in Indianapolis, Indiana, United States (where he also died of a heart attack in 1968), Montgomery came from a musical family, in which his brothers, Monk (string bass and electric bass) and Buddy (vibraphone, and piano), were jazz performers. Although Wes was not skilled at reading music, he could learn complex melodies and riffs by ear. Montgomery started learning guitar in his late teens, listening to and learning recordings of his idol, the guitarist Charlie Christian.
Along with the use of octaves (playing the same note on two strings one octave apart) for which he is widely known, Montgomery was also an excellent single-line or single-note player, and was very influential in the use of block chords in his solos. His playing on the jazz standard Lover Man is an example of his single-note, octave and block chord soloing. (Lover Man appears on the Fantasy album THE MONTGOMERY BROTHERS.)