Cross‐coupling reaction of organogold(I) phosphanes with organic electrophiles in aqueous media has been investigated. Reactions between isolated aryl‐, alkenyl‐, or alkynylgold(I) phosphanes and aryl halides or triflates, alkenyl halides, and allyl acetates proceed under palladium catalysis conditions at room temperature or 80 °C in water with THF as a co‐solvent. The coupling reactions give good yields and are highly versatile and chemoselective, allowing the presence of free amino or hydroxy groups in the electrophile. This methodology was applied to the preparation of substituted phenylalanine esters in a demonstration that gold(I) organometallics are suitable reagents for metal‐catalyzed cross‐coupling reactions under protic conditions.