From very simple to more complex, this is a look at the harmonic structure of the blues. Only a few easy chord forms are used, so you can focus on the basic concepts. I encourage you to explore your instrument further.
Basic blues consists of 3 chord changes. In the key of C, the chords would be
C7, F7, and G7. The chords are derived from the scale. C is the I chord,
F is the IV chord, and G is the V chord. Using the familiar 12 bar
pattern, the basic blues in C would look like this:

Blues 1

By adding some extensions to the basic 7th chords, you can make your rhythm
playing sound more interesting. Adding 9th's, 13th's, and sharp 9th's is common
in blues and jazz.

Blues 1 (variation)

The last two measures of the blues is considered the turnaround. The basic
turnaround we've seen so far is:
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To add harmonic interest to this basic turnaround, precede the G7 with a D7.
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To add more harmonic interest, A7 will precede D7. This creates the standard
I, VI, II, V turnaround.
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Now add some extensions to the basic 7th chords.

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Now you see how the standard I, VI, II, V chords can be substituted
for the I, V turnaround. The same thing can be done in bars 7 thru 10.

The F#dim (diminished) chord can be used to connect the IV chord to
the I chord. Another good way to connect chords is the half-step
substitution. You precede a new measure by starting a half-step above or below
the chord in the next measure. The fingerings are the same, just move the chord
shape up or down the fretboard. For B13 just play C13 down 1 fret. F#9 is F9 up
1 fret. Bb13 is C13 down 2 frets. Anyway, you get the idea.

Blues 3

Half-step substitutions can also be used to add more interest to the turnaround,
also creating a "walking bass line" sound.
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The IImin7 and V7 chords are derived from the degrees of the
major scale. That means, G7 is the V chord and Dmin7 is the II
chord in the C scale. This is usually called a II V progression. This is
a common use of the II V substitutions in a blues progression.

Blues 4

A substitution often used by jazz musicians is replacing a chord with one a
flat fifth away. That is, Eb is the b5 of A, and Db is the b5 of G, etc. Here
are three examples of how the turnaround can be played.

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Of course, you need to be able to play in all 12 keys (easier said than done). After you've learned how to alter the blues, let your ears guide you as to which of the substitutions to use. More often than not, it's best to play the most basic approach. (You mean I learned all this for nothing!) It all depends on the situation. Get out and play, because there is no substitute for experience... it is the best teacher.
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