A series of potassium aryloxides (KOAr) were isolated from the reaction of a potassium amide (KN(SiMe3)(2)) and the desired substituted phenoxide (oMP, 2-methyl; oPP, 2-iso-propyl; oBP, 2-tert-butyl; DMP, 2,6-di-methyl; DIP, 2,6-di-iso-propyl; DBP, 2,6-di-tert-butyl) in tetrahydrofuran (THF) or pyridine (py) as the following: {([K(mu(4)-OMP)(THF)][K(mu(3)-OpP)(4)- (1), {[K-6(eta(6),mu(3)-oMP)(4)(eta(6), mu(4)-oMP)(2)(py)(4)] . [K-6(eta(6), mu(3)-oMP)(6)(eta(6),mu(4-)oMP)(2)(py)(4)].[K-6(eta(6),mu(3)-oMP)(6)(eta(6) (3), {K-4 (eta(6),mu(3)-oPP)(2)(mu(3)-oPP)(2)(py)(3)}(infinity) (4), [K(mu(3)-oBP)(THF)](6) (5), {K-6(eta(6),mu(3)-oBP)(2)(mu(3)-oBP)(4)(py)(4)}(infinity) (6), {K-3(eta(6),mu(3)-DMP)(2)(mu-DMP)(THF)}(infinity) (7), {[K(eta(6),mu-DMP)(py)](2)}(infinity) (8), {K(eta(6),mu-DIP)(infinity) (9), K(eta(6),mu-DBP)}(infinity) (10). Further exploration of the aryl interactions led to the investigation of the diphenylethoxide (DPE) derivative which was isolated as [K(mu(3)-DPE)(THF)](4) (11) or [K(mu(3)-DPE)(py)](4).py(2) (12) depending on the solvent used. In general, the less sterically demanding ligands (oMP, oPP, oBP, and DMP) were solvated polymeric species; however, increasing the steric bulk (DIP and DBP) led to unsolvated polymers and not discrete molecules. For most of this novel family of compounds, the K atoms were pi-bound to the aryl rings of the neighboring phenoxide derivatives to fill their coordination sites. The synthesss and characterization of these compounds are described in detail.