Well, to calculate the electrostatic potential is defined only up to some constant. This is due to the definition: [itex]\vec{E}=-\vec{\nabla}V[/itex]. Physically, that means that you can never measure the potential at a point; only the difference in potential between two points can be measured. Typically, when physicists speak of the potental at a point, they mean 'the potential at a point relative to some agreed upon reference point'. Often one takes the reference point to be infinity (i.e. Very very far away from the field point you are interested in) and defines the potential to be zero there. But, you can define the refernence point to be anywhere you like, and the reference potential to be any value you like; so it is true that you can always define the potential to be zero at some point of interest, but that affects the potential everywhere else which is measured relative to that point. So whether or not the potential is zero wherever E=0 depends on where you have set your reference point.