Herein, we present the synthesis of two pyrene‐functionalized clusters, [(RpyrSn)4S6]⋅2 CH2Cl2 (4) and [(RpyrSn)4Sn2S10]⋅n CH2Cl2 (n=4, 5 a; n=2, 5 b; Rpyr=CMe2CH2C(Me)N‐NC(H)C16H9), both of which form in reactions of the organotin sulfide cluster [(RNSn)4S6] (C; RN=CMe2CH2C(Me)N‐NH2) with the well‐known fluorescent dye 1‐pyrenecarboxaldehyde (B). In contrast, reactions using an organotin sulfide cluster with another core structure, [(RNSn)3S4Cl] (A), leads to formation of small molecular fragments, [(RpyrCl2Sn)2S] (1), (pyren‐1‐ylmethylene)hydrazine (2), and 1,2‐bis(pyren‐1‐ylmethylene)hydrazine (3). Besides synthesis and structures of the new compounds, we report the influence of the inorganic core on the optical properties of the dye, which was analyzed exemplarily for compound 5 a via absorption and fluorescence spectroscopy. This cluster was also used for exploring the potential of such non‐volatile clusters for deposition on a metal surface under vacuum conditions.