We describe the development of a reliable catalytic protocol for peptide bond formation that is generally applicable to natural and unnatural α-amino acids, β-amino acids, and peptides bearing various functional groups. A 10 mol % loading of HSi[OCH(CF3)2]3 as a catalyst was sufficient to guarantee a consistently high yield of the resulting peptide. This method facilitates the sustainable utilization of natural resources by using a catalyst and an auxiliary based on earth-abundant silicon.