AbstractThree new derivatives of methoxyphenyl‐substituted bis(picolyl)phosphines 3–5, the CH2TMS substituted bis(picolyl)phosphine (6) and related phosphine oxides 2b–5b have been synthesized. Syntheses were accomplished by reacting the corresponding dichlorophosphines with picolylTMS (7). An improved synthesis of most of the starting materials is also presented and enables increased ligand yields in all cases. The new bis(picolyl)phosphines and phosphine oxides are extensively characterized by 1H, 13C and 31P NMR spectroscopy and, in the case of the literature known tris(picolyl)phosphine (2) and its new phosphine oxide derivative, single‐crystal X‐ray analysis was applied to structure elucidation efforts. The determination of the molecular structure of (o‐methoxyphenyl)dichlorophosphine (3a) was achieved by X‐ray analysis of a co‐crystal consisting of 3a and its rare phosphonic anhydride derivative 8.