Using high-resolution, lifetime removed, x-ray absorption spectroscopy at the As K edge, we evidence the strong sensitivity of the As electronic structure upon electron doping with Co or pressure change in BaFe2As2, at room temperature. Our results unravel the prominent role played by As-4p orbitals in the electronic properties of the Fe pnictide superconductors. We propose a unique picture to describe the overall effect of both external parameter doping and pressure, resolving the apparent contradiction between angle-resolved photoemission spectroscopy, transport, and absorption results, with the As-p states as a key ingredient.