This is probably the first report on kaolin flocculation done with aqueous guar gum (GG) at various pH. Dynamic light scattering and reduced viscosity proved the polyelectrolytic feature (zeta potential) of aqueous GG which changed on changing pH. Interestingly, the molecular size of GG did not always increased with rising zeta potential due to strong intermolecular repulsion leading to macromolecular recoiling. Best pH range for settling was 4.0-5.0 which included isoelectric point (IEP) of kaolin. Post-settling turbidity was also acceptable at that range. Optimized GG was further blended with oligomeric poly (vinyl alcohol) (PVA) (Mn 14,000) to prepare a new set of flocculant. Oligomeric PVA was previously optimized at similar pH as excellent kaolin flocculant in our earlier investigation. All GG-PVA blends including neat GG exhibited faster settling than neat PVA. However, settling times of all blend compositions were slightly greater than that of neat GG except for few cases where the post settling turbidity was found significantly lower than all our previous investigations. © 2013.