Nd3+ and Eu3+ doped NaNbO3 and Na0.5K0.5NbO3 nanostructured multiferroics (nanoparticles or nanorods) were prepared by a sol-gel route. X-Ray powder diffraction results evidence that the sodium and mixed sodium-potassium niobates show orthorhombic (Pmc21 space group), and monoclinic structure (Pm space group), respectively, confirmed by the Raman spectra. The local structure around the trivalent lanthanides was investigated with Extended X-ray Absorption Fine Structure spectroscopy at the Ln-K edge and luminescence spectroscopy. The Ln3+ ions enter the structure by substituting the alkali metals, with a 12-fold oxygen coordination, and inducing a large amount of static disorder. The visible emission bands of the Eu3+ ions indicate that multiple sites exist for the lanthanide ions, in agreement with the EXAFS results showing the largest amount of static disorder in these samples. A possible indication of clustering of oxygen vacancies around the LnNa″ defect is obtained by VBS calculations