Recent years have seen molybdenum oxide quantum dots (MoOx QDs) as a booming material due to their attractive physical and chemical properties. However, there is still a large demand for MoOx QDs with long-wavelength emission by a facile strategy but these are more challenging to obtain. Herein, we rationally designed and successfully prepared nitrogen and phosphorus co-doped green emitting MoOx QDs (N,P-MoOx QDs) through a microwave-assisted rapid method. They exhibit a maximum emission at 500 nm under a 430 nm excitation. Moreover, by controlling their sizes in the process, we find that such a strategy enables the tuning of the emission color of N,P-MoOx QDs from green to blue. N,P-MoOx QDs show a significant fluorescence response to pH changes, and also display pH-sensitive near-infrared localized surface plasmon resonance (LSPR) at 866 nm. An effective and simple pH probe with a dual-signal response is achieved using N,P-MoOx QDs. As environmental sensors, N,P-MoOx QDs can be applied for sensitive detection of the concentrations of permanganate and captopril, offering the linear range from 0.08 to 25 μM and 0.1 to 31 μM, respectively. Benefitting from the effect of doping nitrogen and phosphorus, the probe could detect a wide range of pH changes (2-9) and is endowed with superior biocompatibility. Further, it is successfully used to "see" the intracellular pH variation by fluorescence confocal imaging. These findings not only demonstrate the achievement of a promising multifunctional probe for biosensing and environmental detection, but also pave the way for the fabrication of transition metal oxide QDs with tunable optical properties.