Complexes of the type [Ru(N-N)(2)(bxbg)]Cl(2) where N-N is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), dipyrido [3,2-d:2',3f] quinoxaline (dpq) (3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4) which incorporate the bis(o-xylene)bipyridine glycoluril (bxbg) as the ancillary ligand have been synthesized and characterized by IR, NMR, UV-visible, luminescence, ESI-MS, cyclic voltammetry, and spectroelectrochemistry. The bis(o-xylene)bipyridine glycoluril initiates a head to head association which act as the nucleation point for the further growth in two direction by head-to-head and tail-to-tail self-association resulting in formation of aggregates in water which have been investigated by (1)H NMR, NOESY, steady state luminescence dilution experiments, and electron microscopy studies. The self-association has been confirmed by single crystal X-ray analysis of complex 2. Electrochemical and spectroelectrochemical studies in acetonitrile show that these complexes undergo reversible one electron oxidation from Ru(II) to Ru(III). The binding of these complexes with calf thymus DNA (CT-DNA) has been studied by absorption titration, steady-state and time-resolved emission measurement experiments, to investigate the influence of the ancillary ligand. The binding ability of these complexes to DNA is dependent on the planarity of the intercalative polypyridyl ligand which is further affected by the bis(o-xylene)bipyridine glycoluril ancillary ligand.