Mixed-ligand lead(II) complexes with 2,2′-bipyridyl and [B10H9OH]2− or monosubstituted hydroxy-substituted closo-decaborate anions with a pendant hydroxy group, separated from the boron cage by an alkoxylic spacer of different lengths [B10H9O(CH2)xO(CH2)2OH]]2− (x = 2 or 5) have been synthesized. Compounds have been characterized by IR and multinuclear NMR spectroscopies. The structures of binuclear complex [Pb(bipy)2[B10H9OH]]2·CH3CN (1·CH3CN), mononuclear complex [Pb(bipy)2[B10H9O(CH2)2O(CH2)2OH]]·0.5bipy·CH3CN (2·0.5bipy·CH3CN), and polymeric complex [Pb(bipy)[B10H9O(CH2)5O(CH2)2OH]]n (3) have been determined by single-crystal X-ray diffraction. In all three compounds, the co-ordination polyhedra of lead(II) are formed by N atoms from two bipy molecules, O atoms of the substituent attached to the boron cage, and BH groups of the boron cage.