Let me clarify my question. Do you mean that when playing a pentatonic scale you can play ANY of the minor modes (lydian, phrygian e.t.c) to add color? Would it sound good or does it depend on the context?
It's ALL context.

What I'm saying is that all of his licks are centered around Em pentatonic (and some around Em diatonic/G major diatonic). Everything he's playing is wanting to resolve to an E root. This is cool on the Em, G and Am chords as they're all in the key of e minor (or G major, take your pick). The F chord, though, is a bit of a substitution and outside of the key of Em or G, diatonically speaking. Playing Em pentatonic over the F chord is very safe. Very vanilla. To me, the soloing doesn't go anywhere after a short time...although at 6:30 he does change the tonality just a bit, but then he goes back to being safe.
If I were king

what I'd do is play licks from the F lydian scale over that F chord. Not only does this add a few different notes that are not being played in the Em pent. wanking, it changes the tonality to the key of C (F lydian is the 4th scale degree of C major). F lydian would work over the Am chord, too.
When playing pentatonic minor you can NOT play just any of the minor modes, but the inverse is somewhat true; when playing phrygian, dorian or aeolian mode you CAN play pentatonic minor. You can NOT for locrian. Where you play the various modes depends on the chord and resolution of the chord.
All this stuff aside, the guy is jamming his heart out and there's a lot of what he's doing that'd be great inspiration for those looking to adopt this style into their playing.