The reactivity of the geminal frustrated Lewis pair (FLP) (F 5 C 2 ) 3 Sn-CH 2 -P(tBu) 2 ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H 3 CC(O)-CH=CH 2 , Ph[C(O)] 2 Ph, PhN=NPh and Me 3 SiCHN 2 ), featuring polar or non-polar multiple bonds and/or represent alpha,beta-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In case of benzil, the reac-tion does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu) 2 PCH 2 -transfer to a prochiral keto func-tion of benzil. All adducts of 1 were characterised by means of multi-nuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments. © 2020 Wiley-VCH GmbH.