Three cyclophanes with the formula (C28H31PS3)n, where n = 1 or 2, were isolated from the base‐promoted macrocyclization of tris(2‐mercaptophenyl)phosphine (4) and tris(3‐bromopropyl)methane (5). Spectroscopic and X‐ray analysis showed them to be the in,in‐isomer 1, the in,out‐isomer 2, and a dimeric in,out,in,out‐isomer 3. Compounds 1 and 3 display approximately C3‐symmetric and Ci‐symmetric structures, respectively, in the crystal, but compound 2 adopts two distinct low‐symmetry conformations in the solid state. In each case, the observed structures correspond to the lowest energy conformations of their respective isomers as calculated at the B3PW91/6‐31G(d) level of theory. The in,in‐isomer 1 displays a close contact between the phosphine in‐lone pair and the in‐methine group, with through‐space spin–spin coupling constants of JPH = 9 Hz and JPC = 24 Hz, the latter of which appears to be the largest reported phosphorus‐carbon through‐space coupling constant.