For the treatment of internal and external hemorrhoids, policresulen (POL) and cinchocaine hydrochloride (CIN) are used in combination. Using a new, simple, fast, and economical first-derivative synchronous fluorescence spectroscopic process, both drugs were simultaneously determined and validated. At Δλ60 nm and with a scanning rate of 600 nm/min, methanol was used as the solvent for both products. In the concentration ranges of 5.0-21.0 μg mL-1 and 0.5-6.0 μg mL-1 for POL and CIN, the amplitude-concentration plots were rectilinear. The detection limits were found to be 0.770 μg mL-1 and 0.118 μg mL-1 and the quantitation limits for POL and CIN were 2.541 μg mL-1 and 0.391 μg mL-1. To evaluate all compounds in synthetic mixtures and medicinal dosage types, the proposed method has been successfully applied. These findings were in line with the results obtained using high-performance thin layer chromatography, the comparison process.