In this work, we synthesized a series of novel carbon dots (CDs) by using phenylenediamines (three isomers: o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine) as starting materials via facile solvothermal approach. As-prepared CDs could emit bright blue, green, yellow, orange, and red light with relatively high PLQY, individually. Optical properties could be controlled by simply varying reaction parameters. The luminescent mechanism was investigated and analyzed in detail. Finally, the blue-emitting CDs and green-emitting CDs showed many appealing properties, such as high sensitivity (limit of detection = 4.52 and 3.50 nmol/L), quick response (<2 minutes), broad response window (0-70 nmol/L), and excellent selectivity for detecting Cr6+ and Al3+ cations, respectively. Thus, they have potential to be developed as the corresponding optical probes. While as-prepared orange-emitting CDs could be applied as a bio-imaging reagent due to its long-wavelength emission, relatively high PLQY, low toxicity, excellent water solubility, and good biocompatibility.