Recently, red emissive carbon dots (R-CDs) have drawn widespread attention on account of their desirable fluorescence properties and good biocompatibility. Despite great efforts, facile synthesis of R-CDs for cellular imaging remains challenging and the fluorescence mechanism of R-CDs is still elusive. Herein, p-phenylenediamine-derived R-CDs with excitation-independency were successfully obtained through a facile solvothermal approach together with proportional precipitation. The fluorescent solvatochromism of R-CDs is realized, while high polarity leads to higher degree of dipole interaction between R-CDs and different solvents, favoring for emissive red-shift. Furthermore, density functional theory is adopted to explore the optical and electronic characteristics of some polycyclic aromatic molecules. Among different configurations, pyridine nitrogen and carbonyl bonds could relatively increase the charge density and significantly narrow the band gap, which can provide a crucial theoretical basis for the precise preparation of R-CDs. Moreover, R-CDs possess favorable cellular imaging ability, which indicates their potential for a promising candidate as fluorescence probes in bioimaging.