Ultrasonic systems must be able to produce an acoustic field with the highest possible energy concentration in sonochemical reactors to accomplish maximum efficacy in the sonolytic degradation of water contaminants. In the present study, the impact of cylindrical and conical stainless-steel reflectors placed on the liquid surface on the sonochemical oxidation activity of ultrasonication reactors was investigated. The amount of effective acoustic power transferred to the ultrasonicated medium without and with reflectors was measured by calorimetric characterization of the sono-reactors at diverse ultrasonication frequencies in the interval of 300–800 kHz and different electrical powers in the range of 40–120 W. Iodide dosimetry without and with reflectors at diverse ultrasonication conditions (300–800 kHz and 40–120 W) and various aqueous solution volumes in the range of 300–500 mL was used to assess the sonochemical oxidation activity, i.e., the generation of oxidative species (mainly hydroxyl radicals). Sonochemiluminescence (SCL) imaging was used to study the active acoustic cavitation bubbles distribution in the sono-reactors without and with reflectors. Significant impacts of the position and shape of the reflectors on the active acoustic cavitation bubble distribution and the sonochemical oxidation activity were observed due to remarkable modifications of the ultrasonic field by directing and focusing of the ultrasonic waves. A significant augmentation in the triiodide formation rate was obtained in the presence of the conical reflector, especially at 630 kHz and 120 W (60.5% improvement), while iodide oxidation was quenched in the presence of the cylindrical reflector at all ultrasonication frequencies and powers. The SCL images show a noteworthy modification in the ultrasonic field and the acoustic cavitation bubble population when reflectors were used. The sonochemical oxidation activity was improved by the conical reflector when placed in the Fresnel zone (near field region).