Three Ln-based 2D metal organic frameworks with the formula [Ln(3,5-DSB)(Phen)] (Ln = La, Pr, Nd; 3,5-DSB = 3,5-disulfobenzoate; Phen = 1,10-phenathroline) were hydrothermally synthesized. They belong to two 2D structural types, and their nets own a different topologies. The isostructural La and Pr compounds possess a uninodal 5-connected SP 2-periodic net (6,3). The Nd compound has a binodal 3- and 6-connected kgd net. The novel compounds exhibit excellent catalytic activities toward the cyanosilylation reaction under solvent-free conditions.