This study investigated a method to determine an efficient operating condition for the process. The OH radical scavenging factor is the most important factor to predict the removal efficiency of the target compound and determine the operating condition of the process. To rapidly and simply measure the scavenging factor, Rhodamine B (RhB) was selected as a probe compound. Its reliability was verified by comparing it with a typical probe compound (para-chlorobenzoic acid, pCBA); the difference between RhB and pCBA was only 1.1%. In a prediction test for the removal of Ibuprofen, the RhB method also shows a high reliability with an error rate of about 5% between the experimental result and the model prediction using the measured scavenging factor. In the monitoring result, the scavenging factor in the influent water of the pilot plant was changed up to 200% for about 8 months, suggesting that the required UV dose could be increased about 1.7 times to achieve 90% caffeine removal. These results show the importance of the scavenging factor measurement in the process, and the operating condition could simply be determined from the scavenging factor, absorbance, and information pertaining to the target compound.