Tetrachloro- and tetraazide-substituted all-cis-tetraphenylcyclotetrasiloxanes (all-cis-T4) 2 and 3 were synthesized in high yields and were fully characterized. Then the precursor 3 underwent CuAAC click reaction with monopropargyl BINOL 4 and dipropargyl BINOL 6 to give the novel BINOL and triazole-containing all-cis-T4 cyclic siloxane 5 and the 29-8-29-membered-ring ladder-type hybrid siloxane 7. The sensing ability of compounds 5 and 7 towards anions was studied as well, and it was observed that 7 could selectively recognize iodides through synergistic C-H⋯I hydrogen bonding, resulting in an impressive fluorescence quenching with a Ksv of 8.10 × 104 M-1.