Highly fluorescent N-doped graphene quantum dots (NGQDs) and graphitic carbon nitride quantum dots (CNQDs, g-C3N4) were synthesized using a solid-phase microwave-assisted (SPMA) technique. The SPMA method, based on the pyrolysis of citric acid and urea with different recipes, is capable of producing quantum dots with coexisting NGQDs and CNQDs at 280 °C within only five minutes. The photoluminescence (PL) emissions from NGQD and CNQDs are strongly dependent on the excitation wavelength and the solvent type, i.e., water, ethanol, and N-methyl pyrrolidinone. The unique attribute of the quantum dots, possessing a multiple chromophoric band-gap structure, originates from the presence of g-C3N4, defect-related emissive traps, and grain boundaries. Thus, an appropriate excitation wavelength induces a conjugated π electron system to fulfill the most probable absorption band, resulting in wavelength-dependent emissions including ultraviolet, visible and infrared light. The quantum yield of the NGQD and CNQD samples can reach as high as 68.1%. Accordingly, a light-emitting device using the combination of the NGQD and CNQD powder embedded polymeric film can emit white-like light with ultra-high power-conversion efficiency.