Many approaches to introduce the CF2P(O)(OR)2 unit into organic molecules make use of CuI‐catalyzed couplings between organic halides and BrZnCF2P(O)(OR)2. Despite the great importance of this process for the synthesis of α,α‐difluoromethylenephosphonates, the constitution and molecular structures of the organozinc precursor and the catalytically relevant copper/zinc complex are still unknown. Here we report on the isolation of these two species, their spectroscopic characterization, and the determination of their structure by single‐crystal X‐ray diffraction. First orienting experiments on the stability of the cuprate reagent in solution at room temperature as well as its reactivity towards allyl bromides were subsequently performed.