Tetrasubstituted　all-carbon　olefins　and　1,3-diene　derivatives　play　a　key　role　in　various　fields.　The　application　of　phosphine-containing　compounds　covers　a　wide　ground　as　well.　Despite　the　importance　of　phosphine-containing　tetrasubstituted　acyclic　unsymmetrical　all-carbon　olefins,　no　general　method　exists　for　the　construction　of　them　stereoselectively.　Herein,　we　present　a　strategy　that　constructs　such　compounds　along　with　1,3-diene　motifs　in　the　presence　of　palladium　catalysis　via　three-component　reaction.　In　addition,　downstream　transformations　upon　reduction　indicated　that　these　products　are　potential　novel　ligands.　This　is　a　ligand-free　process　that　features　broad　substrate　scope　and　various　functional　group　tolerance　with　excellent　stereoselectivity;　of　note,　the　substrates　incorporating　complex　molecules　or　pharmaceuticals　can　also　proceed　smoothly　in　our　protocol.