std::vector<char> * p = &theVec[0];
If you want a pointer to the first char, then:
char * p = &theVec[0][0];
However, be careful, because repeating this pointer past the first subvector will not lead it to the next vector, as would happen with a multidimensional array. To get a pointer to the header of the following sub-vector, you should use:
p = &theVec[1][0];
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