Carbon–carbon bond formation, condensation or click chemistry reactions were used to synthesize novel bowl-shaped sumanene–ferrocene conjugates, along with the extended π-electron framework in good yields. For the first time, the present study uses sumanene derivatives tris-substituted at the benzylic positions as the materials to begin the study on the click chemistry or the metal-catalyzed coupling reactions, Suzuki–Miyaura or Sonogashira couplings. The synthesized conjugates exhibited the property of selective recognizing cesium cations. As a result, this led to the development of highly sensitive and selective fluorescent or electrochemical sensors dedicated to the recognition of cesium cations (Cs⁺) in water. We successfully designed the Cs⁺ electrochemical sensors, which exhibited an acceptable limit of detection (LOD) values at 0.05–0.38 μM. Spectrofluorimetry, voltammetry, and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used to perform the selectivity studies. The results revealed that the designed sensors are highly Cs⁺-selective. This work significantly contributes to the design of new methods of sumanene modification. It also provides further information on the electrochemical properties and innovative applications of metallocene-tethered sumanene derivatives.