Carbon dots (CDs) emerge as promising luminescent materials for potential applications in optoelectronics on basis of their merits including low cost, eco-friendliness and strong, color-tunable photoluminescence (PL). However, the research on solid-state emissive CDs is still at the primary stage because of the aggregation-caused quenching (ACQ) of PL and their poor film-formation ability. In this work, we produce CDs with branched-polyethylenimine (b-PEI) chemically functionalized on the surfaces. The thus newly synthesized P-CDs successfully overcome the bottleneck of ACQ effect and display efficient red and NIR emission in aggregate state. Under the excitation of 520 nm, a strong red emission (maxima of 640 nm) with a high photoluminescence quantum yield (PLQY) of 21% was observed for the P-CDs in neat film. Moreover, this design strategy endows the P-CDs with good film-formation ability via solution spin-coating, which significantly increases its value for the film-based optoelectronic devices.