It won't work well or sound good, although no harm will occur. The EL34s will be biased so cold they'll basically be turned off at idle, and you'll get horrible crossover distortion. It might produce an "interesting" sound, but not anything you would normally want.
The other way round - 6L6s with the switch set to EL34 - is what is sometimes recommended to 'warm up' the amp. It should work safely in the Spongy/Tube mode and probably in Spongy/Diode, but I would be very careful about trying it in the Bold/Tube mode, and not risk it in the Bold/Diode mode at all. Ideally you should check the tube current if you're going to try it at all, even in the Spongy/Tube mode. It is possible you could find some very cold-running 6L6s which might be safer than usual, but you'd need to check them in the amp. Don't just "try it" with any normal set of 6L6s.