In recent years, semiconducting polymer dots (Pdots) have emerged as a novel class of extraordinarily bright fluorescent probes with burgeoning applications in bioimaging and sensing. While the desire for near-infrared (NIR)-emitting agents for in vivo biological applications increases drastically, the direct synthesis of semiconducting polymers that can form Pdots with ultrahigh fluorescence brightness is extremely lacking due to the severe aggregation-caused quenching of the NIR chromophores in Pdots. Here we describe the synthesis of dithienylbenzoselenadiazole (DBS)-based NIR-fluorescing Pdots with ultrahigh brightness and excellent photostability. More importantly, the fluorescence quantum yields of these Pdots could be effectively increased by the introduction of long alkyl chains into the thiophene rings of DBS to significantly inhibit the aggregation-caused emission quenching. Additionally, these new series of DBS-based Pdots can be excited by a commonly used 488 nm laser and show a fluorescence quantum yield as high as 36% with a Stokes shift larger than 200 nm. Single-particle analysis indicates that the per-particle brightness of the Pdots is at least 2 times higher than that of the commercial quantum dot (Qdot705) under identical laser excitation and acquisition conditions. We also functionalized the Pdots with carboxylic acid groups and then linked biomolecules to Pdot surfaces to demonstrate their capability for specific cellular labeling without any noticeable nonspecific binding. Our results suggest that these DBS-based NIR-fluorescing Pdots will be very practical in various biological imaging and analytical applications.