Venturi-cascading is a technique to control pollutant emissions from diffusion flames by modifying air infusion and fuel-air mixing rates through changing the flow dynamics in the combustion zone with a set of venturis surrounding the flame. A propane jet diffusion flame at a burner-exit Reynolds number of 5100 was examined with a set of venturis of specific sizes and spacing arrangement. The venturi-cascading technique resulted in a decrease of 33 percent in NO emission index along with a 24-percent decrease in soot emission from the flame, compared to the baseline condition (same flame without venturis). In order to understand the mechanism behind these results, laser-induced fluorescence (LIF) spectroscopy was employed to study the concentration field of the radicals (OH, CH, and CN) in the baseline and venturi-cascaded flames. The LIF measurements, in the near-burner region of the venturi-cascaded flame, indicated an average decrease of 18, 24 and 12 percent in the concentrations of OH, CH, and CN radicals, respectively, from their baseline values. However, in the midflame region, a 40-percent average increase in OH from its baseline value was observed. In this region, CH or CN radicals were not detected. The OH radical concentration in the downstream locations was mostly affected by soot rather than by temperature.