By triple epoxide → cyclopropane transformation starting from cis-benzene trioxide the 3α,6α,9α-tris(TIPS-ethynyl) (1b), -tris(alkoxycarbonyl) (1d, e), -tricyano (1f), and -tris(ammoniomethyl) (1j) derivatives of the still elusive parent cis-[1.1.1]-tris-σ-homobenzene (1a) have been synthesized. Out of a number of carbon nucleophiles tested, a weakly basic mixed cyanocuprate of Li-TIPS-propyne proved the reagent of choice: Eliminations were largely avoided, the scyllo ^[*]-2,4,6-tris(TIPS-propargyl)cyclohexane-1,3,5-triol (13a), obtained in a stereoselective one-pot threefold epoxide opening (up to 69%), allowed the pertinent functional group manipulations. The selectivity of the base-induced triple cyclopropane ring closure in the flexible cyclohexane precursors strongly depends on the activating groups and is promoted by fixation of the "all-axial" conformation as an adamantoid orthophosphate. The ΔG ^≠ values determined for the generally neat 3σ → 3π isomerizations [28.5 (1e), 29.0 (1f), 22.6 (1j) kcal mol ^-1] are in line with concerted reaction courses ([σ2s+σ2s+σ2s]). For the trinitrile 1f an X-ray structure analysis confirmed a nearly planar cyclohexane ring and a relatively large cyclohexane/cyclopropane interplanary angle (113°).