The Heck reaction of OPPh3− n (4-C6H4Br) n (n= 1–3) with electron deficient and neutral olefins led to linear olefin-substituted phenylphosphine oxides, whilst the reaction with an electron rich olefin in an ionic liquid solvent resulted in the formation of acetyl variants. The same bromophenylphosphine oxides also reacted with arylboronic acids under normal Suzuki coupling conditions, affording arylated phenylphosphine oxides in excellent yields. ...