The basic idea, at least as it is taught to the freshmen is as following:
In conductor you have plenty of electrons that are practically "free". You are interested in electrostatic situation, that is the situation in which all electrons are by definition practically still. This is possible only if electric field within conductor is zero. If that would not be so, there would exist electric force
$$\vec{F} = q \vec{E} = m \vec{a}$$
end electrons would accelerate.
By using Gauss law, you can prove, that the core of the conductor is actually charge neutral. Imagine that you make a Gauss surface that encloses all but surface of the conductor (i.e. Gauss surface is only tiny fraction smaller than surface of the conductor). Since electric field on the whole Gauss surface equals zero, that means that
$$\frac{Q}{\epsilon_0} = \int \vec{E} \cdot \text{d}\vec{A} = 0,$$
that is total enclosed charge $Q$ equals zero.
So we came to the final conclusion, which obviously claims that any excessive positive or negative charge (if such exists) must be on the surface of the conductor. Electric field can be (and actually usually is) larger than zero on the very surface of the conductor. This is because electrons, even if they are pushed out by electric field, cannot leave the material, they are not "free" to do that.
Generally all this idea of electrostatics seem to be a bit "over edge", isn't it? Well as it turns out electrons need only a fraction of a second to realign themselves in such a way that electrostatic situation is satisfied. So electrostatic situations are real.