Near-infrared II (NIR-II, 1000-1700 nm) fluorescent imaging (FI) has been reported to achieve optical images with higher resolution and deeper penetration. Among the organic NIR-II small molecules, donor-acceptor-donor (D-A-D) type fluorescent agents have shown superior photophysical and biocompatible properties for FI applications but have ongoing limitations, such as the difficulty in further modifying them with drug-carrying functional groups or prodrugs. In this work, three D-A-D type NIR-II fluorophores with electron acceptors of 4,8-bis(5-bromo-4-(2-octyldodecyl)thiophen-2-yl)-1H,3H-benzo[1,2-c:4,5-c’]bis([1,2,5]thiadiazole) (BBT), 6,7-bis(4-(hexyloxy)phenyl)-4,9-di(thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline (TTQ) and 4,6-bis(5-bromo-2-thienyl)thieno[3,4-c][1,2,5]thiadiazole (TTDT) have been successfully prepared. Their optical and imaging properties and stability were investigated via theoretical and experimental studies. The results demonstrated that TTDT-SF exhibited good NIR-II imaging ability. Importantly, TTDT-SF showed outstanding stability in an alkaline and redox environment. Subsequently, a stable atom transfer radical polymerization (ATRP) initiator, based on TTDT and its derivative water-soluble fluorescent polymer TTDT-TF-POEGMA, synthesized through ATRP, was successfully fabricated. It was demonstrated that TTDT-TF-POEGMA exhibited excellent fluorescence ability, great water solubility, effective light stability and great potential in tumor FI and image-guided surgery. In a word, this work has developed a new stable initiator with NIR-II fluorescent properties, which provides a platform for the development of water-soluble and multifunctional NIR-II fluorescent polymers for a broad range of applications.