We have investigated the doping mechanism of pentacene with iodine and its impact on the structure and on the electronic properties of single crystals, powders, and thin films in a large range of iodine concentration up to six iodine per pentacene (PEN) molecule (I/PEN = 6). Three regimes of doping have been identified. In the low doping regime I/PEN < 0.05, the pristine pentacene structure of single crystals is maintained. Electron spin resonance (ESR) evidences a Pauli susceptibility, that is, the characteristic fingerprint of delocalized holes in the valence band of pentacene. In the intermediate doping regime (0.1 < I/PEN <= 2.0), iodine diffuses between the (a,b) planes of the pentacene structure and forms an intercalate. Charge transfer between iodine and pentacene is witnessed by both UV-vis and IR signatures of PEN⁺ cations and related species, for example, cation dimers (PEN⁺)₂ and typical Raman signatures of the I₃^- and I₅^- species. Spin pairing of pentacene cation radicals is further supported by the observation of a thermally activated behavior of the ESR spin susceptibility. In the heavy doping regime (2 < I/PEN <= 6), all traces of structural order vanish, indicating that iodine penetrates within the (a,b) planes of the intercalate in a disordered manner, forming an amorphous-like material. This high degree of disorder results in increased charge localization. Most spin/charge species are ESR-silent and only a limited fraction (a few percents) exhibits a Curie-like susceptibility. Because of disorder, the macroscopic conductivity of doped pentacene single crystals does not exceed a few S/cm at 300 K