Pure and doped Ba6Ti2Nb8O30 (BTN), obtained by substituting M = Cr, Mn, or Fe on the Ti site (Ba6Ti2-x MxNb8O30, x = 0.06 and 0.18) and Y and Fe on the Ba and Ti sites, respectively (Ba6-xYxTi2-xFexNb8O30, x = 0.18), are synthesized. The influence of cation doping on the local structure, the cation oxidation state, and the possible defect formation able to maintain the charge neutrality are investigated by spectroscopic (electron paramagnetic resonance (EPR) and micro-Raman), structural (X-ray powder diffraction) and transport (impedance spectroscopy, thermoelectric power) measurements, in the temperature range of 300-1200 K in air and N-2 flow. Starting from the valence state of the doping ions (Fe3+, Cr3+, and Mn2+), determined by EPR, and from thermoelectric power measurements, evidencing a negative charge transport, different charge-compensating defect equilibria, based on the creation of positive electron holes or oxygen vacancies and electrons, are discussed to interpret the conductivity results.