Six organic−inorganic hybrid pyridine-4-carboxylate-decorated organotin (OT)−lanthanide (Ln) heterometallic antimotungstates 3+ (2), Pr 3+ (3), Nd 3+ (4), Sm 3+ (5), Eu 3+ (6); Hpca = isonicotinic acid] have been prepared with the help of the structuredirecting effect of the trivacant [B-α-SbW 9 O 33 ] 9− segment toward [(CH 3 ) 2 Sn] 2+ and Ln 3+ ions in an acidic water medium. The prominent architecture characteristic is that their structural units consist of a trivacant [B-β-SbW 9 O 33 ] 9− segment stabilized by three [Sn-(CH 3 ) 2 (H 2 O)] 2+ groups and a [Ln(H 2 O) 6 (pca)] 2+ cation, which are interconnected to propagate an intriguing two-dimensional (2D) network. For all we know, 1−6 stand for the first 2D OT−Ln heterometallic polyoxometalates. Furthermore, luminescence performances of solid-state 3−6 were deeply surveyed at ambient temperature. Energy migration from [B-β-SbW 9 O 33 ] 9− and pca − to Sm 3+ centers in 5 was also studied. Comparative studies demonstrate that the contribution of [B-β-SbW 9 O 33 ] 9− sensitizing the emission of Sm 3+ is prominently larger than that of pca − sensitizing the emission of Sm 3+ in the emission process of 5. Most interestingly, 6 as a fluorescence probe exhibits high selectability and sensitivity for recognizing Zn 2+ and Cu 2+ in water.