Therapies that target the downstream inhibition of gene expression are of great current research significance with considerable efforts now dedicated to the discovery of new antisense oligonucleotides (ASOs). The development of nucleic acid probes targeting DNA, such as triplex-forming oligonucleotides (TFOs), offers an alternative strategy whereby gene expression is directly inhibited at the genomic level. Here, we present a click chemistry strategy for the generation of a new class of cis-platinum(II)-TFO hybrid biomaterial that possess DNA binding and crosslinking activity.