The synthesis and applications of dual- or multi stimuli-responsive polymers have gained increasing attention. One-pot strategy by combination two different polymerization mechanisms is promising for the synthesis of dually stimuli-responsive polymers in a rapid route. In this work, we report a convertible anionic ring-opening and RAFT polymerization by using asymmetrical trithiocarbonate as both an initiator for the anionic ring-opening polymerization and a chain transfer agent for RAFT polymerization to produce poly(propylene sulfide) (PPS)- poly(N-isopropylmethacrylamide) block-like copolymers. Furthermore, the ROS and temperature responsibility of the formed copolymer are also evaluated.