The hydroamination of diphenylbutadiyne with 1 equiv of the secondary amines HNRR' (R/R' = Ph/Ph, Ph/Me, and pTol/Me) in the presence of catalytic amounts of the tetrakis(amino)calciate K2[Ca{N(H)Dipp}4] (Dipp = 2,6-diisopropylphenyl) yields the corresponding 1-(diorganylamino)-1,4-diphenylbut-1-ene-3-ynes as a mixture of E/Z isomers. These tertiary alkenylamines react with diphenylphosphane to form RR'N-C(Ph)═CH-CH═C(Ph)-PPh2 [R/R' = Ph/Ph (1), Ph/Me (2), and pTol/Me (3)] in the presence of catalytic amounts of [(THF)4Ca(PPh2)2] or of the same calciate K2[Ca{N(H)Dipp}4]. Whereas the hydroamination is regio- (amino group in 1-position) but not stereoselective (formation of E and Z isomers), this second hydrofunctionalization step is regio- (phosphanyl group in 4-position) and stereoselective (only E isomers are formed), finally leading to mixtures of (E,E)- and (Z,E)-1-(diorganylamino)-1,4-diphenyl-4-(diphenylphosphanyl)buta-1,3-dienes.