Highly coloured paramagnetic polymer supported lithium 5,5′ and sodium 6,6′ naphthalenide complexes have been prepared from the reaction of THF solutions of lithium and sodium biphenylide with polystyrene bearing –CH2SiMe2(C10H7) groups. Treating chloropropyl functionalised silica, alumina and titania surfaces with H3Al·NMe3 or H3Ga·NMe3 afford hydroxyl depleted surfaces. Successive treatment with lithium biphenylide, 1-(chlorodimethylsilyl)naphthalene and an alkali biphenylide affords supported alkali naphthalenide complexes which generate in high yield lithium and sodium reagents when treated with a range of organic halides, nitriles and phosphates, as found for 6,6′ and 7,7′.