The lyrics of "This Charming Man" comprise a first person narrative in which the male protagonist punctures one of his bicycle's wheels on a remote hillside. A passing "charming man" in a luxury car stops to offer the cyclist a lift, and although the protagonist is at first hesitant, after much deliberation he accepts the offer. While driving together the pair flirt, although the protagonist finds it difficult to overcome his reluctance: "I would go out tonight, but I haven't got a stitch to wear". The motorist tells the cyclist: "it's gruesome that someone so handsome should care".
Morrissey deliberately used archaic language when composing the voice-over style lyrics for "This Charming Man". His use of phrases and words such as 'hillside desolate', 'stitch to wear', 'handsome' and 'charming' are used to convey a more courtly world than the mid-Eighties north of England, and evoke a style that has, in the words of the music critic Mat Snow "nothing to do with fashion". Morrissey had already used the word 'handsome' in a song title—in "Handsome Devil", the B-side to "Hand in Glove"—and observed in a 1983 interview with Barney Hoskyns that he used the word to "try and revive some involvement with language people no longer use. In the daily scheme of things, people's language is so frighteningly limited, and if you use a word with more than 10 letters it's absolute snobbery." Snow puts forward the case that through the use of the dated word 'charming', Morrissey sought to rebel against the then mainstream gay culture from which he felt alienated. Morrissey told Hoskyns: "I hate this 'festive faggot' thing...People listen to "This Charming Man" and think no further than what anyone would presume. I hate that angle, and it's surprising that the gay press have harped on more than anyone else. I hate it when people talk to me about sex in a trivial way."
As with many of Morrissey's compositions, the song's lyrics features dialog borrowed from a cult film. The line "A jumped-up pantry boy who never knew his place" is borrowed from the 1972 film adaptation of Anthony Shaffer's 1970 homoerotic play Sleuth, in which Laurence Olivier plays a cuckolded author to Michael Caine's 'bit of rough'.
Both studio versions begin with an introductory guitar riff, joined by the rhythm section. Morrissey's vocals are first heard eight seconds into the track. His vocal melodies are diatonic, and consciously avoid blues inflections. The chorus is played twice; the first time it is followed by a brief pause, the second by the closing of the song. The rhythm section of Andy Rourke and Mike Joyce provide a beat more danceable than usual for a Smiths track. The drums were originally programmed on a Linn Drum Computer, under the direction of producer John Porter. Porter used the programme to trigger the sampled sounds of the live drum kit, featuring a Motownesque bassline. Marr's guitar part consists of single notes of thirds as opposed to strummed bar chords, and his guitar serves to creates a counter-melody throughout the song. Marr overdubbed numerous guitar parts onto the song, and in a December 1993 interview, told Guitar Player magazine:
I'll try any trick. With the Smiths, I'd take this really loud Telecaster of mine, lay it on top of a Fender Twin Reverb with the vibrato on, and tune it to an open chord. Then I'd drop a knife with a metal handle on it, hitting random strings. I used it on "This Charming Man", buried beneath about 15 tracks of guitar ... it was the first record where I used those highlife-sounding runs in 3rds. I'm tuned up to F# and I finger it in G, so it comes out in A. There are about 15 tracks of guitar. People thought the main guitar part was a Rickenbacker, but it's really a '54 Tele. There are three tracks of acoustic, a backwards guitar with a really long reverb, and the effect of dropping knives on the guitar – that comes in at the end of the chorus.
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