β-Alanine and its derivatives are important starting materials for the preparation of peptides or compounds with biological activity. In this work, the authors are presenting a new approach for the synthesis of N-alkyl-β-amino acids and N-alkyl-β-amino esters using dendrimeric intermediates in a one-pot reaction, with friendly reaction conditions. Dendrimeric compounds, with a pentaerythritol core, were easy prepared and used to obtain the β-amino acid derivatives and β-amino esters with good yields. This paper presents the first reaction where dendrimers are used for synthesizing organic compounds. Spectroscopic characterization by 1H- and 13C-NMR of dendrimers and final products is also presented.