The novel hyperbranced polymers containing reductive groups were successfully prepared and characterized using redox/reversible addition fragmentation chain transfer (RAFT)/self-condensing vinyl polymerization (SCVP) method. Several redox initiating chemicals such as Cu(III)/—CONH

2

Ce(IV)/—CONH

2

and Ce(IV)/—OH were chosen to increase the free radical generating rate

and the chain transfer agent (CTA) was used to reduce the molecular chain propagating rate

in order to obtain polymers with high degree of branching. Detailed analyses based on the molecular weight

α

value and the degree of branching of polymers (DB) obtained from

1

H-NMR spectra and multi detector size exclusion chromatography (MDSEC) suggested the acquiring of hyperbranced polyacrylamides with Cu(III)/—CONH

2

and Ce(IV)/—CONH

2

as initiator in the presence of the CTA. Meanwhile

the as-prepared poly(

N

-hydroxymethyl acrylamide) (PNHAM) with higher DB value (0.48) proved that using Ce(IV)/—OH as the initiator could increase the free radical generating rate and diminish the gap between the propagating rate and the initiation rate during the reaction procedure. In addition

the effect of oxidant concentration on the Mark-Houwink index (

α

) value and the DB was also studied.