Two　isomorphic　titanium-doped　organotin-oxo　aromatic　aldoxime　clusters,　SnTi-1　and　SnTi-2,　have　been　successfully　synthesized　via　a　solvothermal　method.　Both　clusters　have　an　identical　undecameric　core,　consisting　of　a　pentagonal　wheel-shaped　moiety　{Ti5}　and　two　alkylate　trimers　{Sn3}　fused　together,　and　decorated　with　unsubstituted　and　methoxy-substituted　aldoxime　ligands,　respectively.　They　exhibit　excellent　solubility,　chemical　stability,　and　hydrophobicity　owing　to　the　existence　of　peripheral　protective　shells　of　alkyl　and　aromatic　groups.　The　steric　hindrance　effect　of　methoxy　induces　a　rearrangement　of　clusters,　altering　weak　interactions　from　C-H...7c　to　7c...7c　between　cluster　molecules,　and　ultimately　modulating　the　third-order　nonlinear　optical　from　saturation　absorption　to　reverse　saturation　absorption.