Well the entire experience of consciousness is rooted in the brain which is a bioelectrochemical system so yes.
It would be hard to say what causes increased confidence in sober individuals but from looking at what MDMA does you could say higher levels of serotonin, dopamine and norepinephrine, perhaps.
It's a little more complex than that though as although these are the primary observable functions of MDMA in the brain, this causes a cascade of other alterations such as oxytocin release and hormonal changes, and if you look at it from an what happens ultimately on MDMA, going by the recent brain imaging work of David Nutt, what's happening is there is a massive reduction in function of the amygdala, or 'lizard brain'.
So it's hard to say where the effects are coming from, from the actual release of neurotransmitters themselves or from the reduction in functioning of the amygdala that happens as a result.
Also, a more confident sober individual may have this altered brain functioning from the environment they have grown up in and the environment they currently spend their lives in, the kind of things they do and people they spend their time with, they weren't necessarily born that way.