Orthorhombic Lead metaniobate (PbNb2O6) exhibits ferroelectric properties and has a Curie temperature, TC of 570 degrees C. This work reports on investigations made on ferroelectric Lead metaniobate, (PN) and its solid solutions with bismuth and titanium Pb(1-X)BiX(Nb(1-X/2)TiX/2)(2)O-6, (PBTN), bismuth and sodium Pb(1-X)BiX/2NaX/2Nb2O6, (PBNN), bismuth and potassium Pb(1-X)BiX/2KX/2Nb2O6,(PBKN), and calcium and titanium (1-x)PbNb2O6-xCaTiO(2), (PCTN). The ferroelectric polymorph was obtained for all the solid solutions without quenching, and the optimized sintering temperature was reduced with increasing substitution level except in the system PCTN. The lattice parameters of the solid solutions were found to systematically vary with composition. Curie temperature was reduced with increasing substitution level in all the series. Piezoelectric charge constant d33 increases with composition of the solid solutions.