Polymeric methyltrioxorhenium, {(CH3)0.92ReO3}∞ (poly-MTO), is the first member of a new class of organometallic hybrids which adopts the structural pattern and physical properties of classical perovskites in two dimensions (2D). We demonstrate how the electronic structure of poly-MTO can be tailored by intercalation of organic donor molecules, such as tetrathiafulvalene (TTF) or bis-(ethylendithio)-tetrathiafulvalene (BEDT-TTF), and by the inorganic acceptor SbF3. Integration of donor molecules leads to a more insulating behavior of poly-MTO, whereas SbF3 insertion does not cause any significant change in the resistivity. In particular, with increasing donor intercalation the metallic behavior of the parent compound, poly-MTO, becomes surprisingly suppressed leading to an insulator at TTF (BEDT-TTF) donor concentrations above 50% (25%). The resistivity data of pure poly-MTO exhibit a crossover from metallic (dρ/dT > 0) to insulating (dρ/dT < 0) behavior at a characteristic temperature around Tmin ≃ 38 K. Above Tmin the resistivity ρ(T ) is remarkably well described by a two-dimensional electron system. Below Tmin an unusual resistivity behavior, similar to that found in doped cuprates, is observed: The resistivity initially increases approximately as ρ ∼ ln(1/T ) before it changes into a √ T dependence below 2 K. As an explanation we suggest a crossover from purely two-dimensional charge-carrier diffusion within the {ReO2}∞ planes at high temperatures to three-dimensional diffusion at low temperatures in a disorder-enhanced electron-electron interaction scenario (Altshuler-Aronov correction). Furthermore, a linear positive magnetoresistance was found in the insulating regime, which is caused by spatial localization of itinerant electrons at some of the Re atoms, which formally adopt a 5d 1 electronic configuration. X-ray diffraction, IRand ESR-studies, temperature dependent magnetization and specific heat measurements in various magnetic fields suggest that the electronic structure of poly-MTO can safely be approximated by a purely 2D conductor which is labile towards spatial localization of electrons under formation of Re (d 1 ) centers in the presence of a magnetic field.