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This paper report the relationship between B-Al-N doping concentration fluctuation and photoluminescence effects of fluorescent 4H-SiC single crystals. The photoluminescence emission properties, dopant concentration, and internal quantum efficiency of B, Al and N co-doped 4H-SiC are characterized. It is found that the emission spectra exhibit a wide band that covers from about 450 nm to 750 nm. The peak intensity of the emission spectra is strongly affected by B, Al and N concentrations. By further analyses the roles of B-Al-N dopants, a hypothetical formula is proposed, which can help to profile the strong correlation between photoluminescence effects and B-Al-N doping concentrations.