The crystallographic and magnetic behaviors of (Tb1-xNa x)MnO3-y (0 ≤ x ≤ 0.3) have been studied by neutron powder diffraction (NPD), synchrotron X-ray powder diffraction, and Raman spectroscopy techniques. Although Na+ ions have larger ionic radii than Tb3+ ions, analysis of NPD data reveals a decrease in cell volume upon Na-doping, which can be explained solely by the occurrence of oxygen deficiencies and not by the size effect. The Raman spectrum represents the variation in bond length and bond angle, which originates from the balance of ions, asymmetric structure, and defects in the system. Na-doping causes an oxygen deficiency, and consequently, a peak shift is seen in the Raman spectrum because of the structural adjustment resulting from the doping. The observed effective moments decrease with increasing x because of the replacement of Tb3+ ions by Na+ ions. The well-defined peak at ∼45 K (labeled TMn) of the x = 0.3 sample is associated with Mn spin ordering, while the magnetic responses associated with TMn are not clearly present in the x = 0.15 and x = 0 samples.