In the process of studying the chemistry of perfluoro2.2paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron‐donor character and size. Quantum chemical calculations, performed at the HF/6‐311 + G(d,p)//B3LYP/EPR‐III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four‐ and five‐bond 19F19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd. The pattern of coupling constants in perfluoro2.2paracyclophanes (PFPCs) indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent size and electron‐donor character. Quantum chemical calculations confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four‐ and five‐bond 19F19F couplings are discussed in detail.