Tri(1-naphthyl)phosphine (Np₃P) has been easily prepared in 34% yield from red phosphorus and 1-bromonaphthalene in the superbasic system t-BuONa/DMSO. The expedient procedures for the synthesis of aryl acetylenes by Sonogashira coupling of aryl iodides with terminal alkynes using Np₃P as a ligand have been developed. For the first time, it is found that the reaction with compounds containing electron-donating substituents preferably affords buta-1,3-diynes.