A new series of niobates A6n+[Bxm+Nb12-x]Nb4O42(A=K,Ba;B=Ni,Cr,Fe,Ti and Zr) has been synthesized by solid state reaction and the flux method. The morphology, optical properties and chemical stability of the new compounds were studied. The composition of the compounds were determined by chemical analyses and electron probe X ray microanalysis(EPMA). The results of X ray powder diffraction(XRPD) analyses confirmed that the compounds crystallized in the hexagonal system with space group P63/mcm(193), and which are isostructure with K6CrNb15O42. X ray powder diffraction lines for these compounds were well indexed.