The reactivity of bis-TMS-substituted C,C-diacetylenic phosphaalkene (A(2)PA) 1 in Sonogashira-Hagihara cross-coupling reactions has been examined. The selective and successive deprotection of the two silyl groups in 1 is enabled by the steric bulk of the Mes* group which renders the acetylene trans to Mes* more reactive and thereby facilitates selective and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(i)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A(2)PA linked by a phenylene spacer. cis-trans Isomerization across the P[double bond, length as m-dash]C bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A(2)PAs. The introduced aryl groups are integral parts of the entire π-system as evidenced by spectroscopic and electrochemical studies.