Peptide nucleic acids (PNA) have received great attention as tools in molecular biology and biotechnology, diagnostic agents, and potential antisense drugs. Many derivatives and analogues of PNA were designed and prepared to improve their physico-chemical and biological properties. In most cases, PNA oligomers were synthesized by peptide synthesis from N-protected monomers. In this work, a new method to obtain PNA monomers and PNA chain prolongation by Ugi four-component condensation reaction was tested by synthesizing PNA monomers and dimers. This method differs from classical peptide chemistry in that no prior preparation of PNA monomers is needed as they are built up along with the extension of chain. The synthesis of the key component isocyanide is also presented.