Green-emissive carbon quantum dots (CQDs) with exclusive chemosensing aspects were synthesized from orange pomace as a biomass-based precursor via a facile microwave method without using any chemicals. The synthesis of highly fluorescent CQDs with inherent nitrogen was confirmed through X-ray diffraction, X-ray photoelectron, Fourier transform infrared, Raman, and transmission electron microscopic techniques. The average size of the synthesized CQDs was found to be 7.5 nm. These fabricated CQDs displayed excellent photostability, water solubility, and outstanding fluorescent quantum yield, i.e., 54.26%. The synthesized CQDs showed promising results for the detection of Cr 6+ ions and 4-nitrophenol (4-NP). The sensitivity of CQDs toward Cr 6+ and 4-NP was found up to the nanomolar range with the limit of detection values of 59.6 and 14 nM, respectively. Several analytical performances were thoroughly studied for high precision of dual analytes of the proposed nanosensor. Various photophysical parameters of CQDs (quenching efficiency, binding constant, etc.) were analyzed in the presence of dual analytes to gain more insights into the sensing mechanism. The synthesized CQDs exhibited fluorescence quenching toward incrementing the quencher concentration, which was rationalized by the inner filter effect through time-correlated single-photon counting measurements. The CQDs fabricated in the current work exhibited a lower detection limit and a wide linear range through the simple, eco-friendly, and rapid detection of Cr 6+ and 4-NP ions. To evaluate the feasibility of the detection approach, real sample analysis was conducted, demonstrating satisfactory recovery rates and relative standard deviations toward the developed probes. This research paves the way for developing CQDs with superior characteristics utilizing orange pomace (biowaste precursor).