The tris(pentafluorophenyl)borane (B(C6F5)3)-catalyzed group transfer polymerization (GTP) of N,N-disubstituted acrylamide (DAAm) using a moisture-tolerant hydrosilane (HSi) as part of the initiator has been intensively investigated in this study.The screening experiment using various HSis suggested that dimethylethylsilane (Me2EtSiH) with the least steric bulkiness was the most appropriate reagent for the polymerization control.The chemical structure of the DAAms significantly affected the livingness of the polymerization.For instance,the polymerization of N,N-diethylacrylamide (DEtAAm) using Me2EtSiH only showed better control over the molecular weight distribution,while that of N-acryloylmorpholine (MorAAm) with a more obstructive side group using the same HSi afforded precise control of the molecular weight as well as its distribution.