Various oligoarene-type phosphines having a hydroxy group were synthesized based on a two-step repetitive method that we developed, and these phosphines were used as ligands for palladium in catalytic cross coupling with Grignard reagents. The study revealed that a hydroxylated terphenylphosphine accelerated the rate of the cross coupling of o-bromophenol and exhibited preference for the ortho-isomer over the meta- and para-isomers.