Two tetraphenylethene-based tetracationic dicyclophanes 1 and 2 were synthesized via a one-step SN2 reaction. Based on the central TPE unit and the slight difference of the outer linkers, 1 and 2 exhibited a classic aggregation-induced emission but contrasting mechanochromic luminescence under grinding, vaporing, or hydrostatic pressure in the solid state, and photochemical reactions with various emitting colours induced by photoirradiation in the solution state.