Homogenous catalysis is an essential tool within the commercial manufacture of bulk and fine chemicals. Within this, phosphine ligands, such as tricyclohexylphosphine, otherwise known as CYTOP® 366, are a crucial component. When designing a pathway to your ligand of choice, some key considerations include safety, yield and quality, but at commercial volumes we must also balance cost and consider the technologies readily available. Herein, we report the synthetic route that was chosen to manufacture tricyclohexylphosphine at commercial scale. We also consider, with the use of computational calculations, why traditional hydrophosphination methods failed, where the selected pathway succeeded.