First amino bis(picolyl) and amino bis(quinaldinyl) phosphines were synthesized by reaction of the corresponding amino dichlorophosphines – the new carbazolyl dichlorophosphine (1) and diisopropylamino dichlorophosphine (2) with either picolylTMS (6), quinaldinylTMS (15) or their respective lithium derivatives 12 and 16. The deviation of the standard synthesis via the silyl route is necessary for the synthesis of the diisopropylamino derivatives 11 and 14 due to the fact that compound 2 is not reacting with 6 or 15 even at reflux conditions. All new compounds are extensively characterized by multinuclear NMR spectroscopy and some also by single crystal X-ray diffraction. Also the molecular and crystal structure of the new dichlorophosphine 1 was determined.