Peptide Nucleic Acids (PNA) are DNA analogues with nucleobases linked to a pseudopeptide backbone instead of sugar-phosphate backbone and show sequence specific binding to complementary DNA and RNA with high affinity. We have now developed “Janus PNAs” that carry two nucleobases in each PNA monomer, leading to two different sequences on either face of Janus PNA. The additional nucleobase in each monomer is linked at C• or C• through an alkyl chain. Heren a new type of Janus PNA analogue – “diacyl hydrazine PNA” in which both nucleobases are attached by t-amide linkage is presented. This exhibits association and dissociation very different from the earlier C•/C• Janus PNAs and such polyplex complexes offer new opportunities for multiple gene silencing and in material applications.