Potassium bromate (KBrO3), employed ubiquitously as an oxidizing agent in commonly consumed baked foods and as a flour improver to enhance dough quality, has been recognized as a possible human carcinogen. Despite stringent prohibitions in numerous nations eliciting substantial apprehension worldwide, notably in Bangladesh, the pervasive occurrence of KBrO3 in baked foods persists as a formidable public health quandary. This study aimed to investigate the presence of KBrO3 in five different popular baked foods comprising a total of 104 samples, such as bread (n = 39), cake (n = 33), burger buns (n = 13), pizza (n = 10), and naan (n = 9), collected from different districts across Bangladesh. The amounts of KBrO3 were quantified using UV–visible spectrophotometric method. A calibration curve was obtained with a satisfactory linearity and a correlation coefficient (R2) 0.998. The sensitivity was confirmed by limits of detection (LOD = 0.0180 mg L−1) and quantification (LOQ = 0.0548 mg L−1). The recovery rates for spiked samples were 87%–103%, ensuring the accuracy and reliability of the measurements. KBrO3 concentrations varied significantly across the samples: BDL to 5.53 ± 0.24 mg kg−1 in breads, BDL to 6.18 ± 0.01 mg kg−1 in cakes, 0.86 ± 0.01 to 1.69 ± 0.01 mg kg−1 in burger buns, 0.92 ± 0.01 to 4.35 ± 0.01 mg kg−1 in pizzas, and BDL to 5.37 ± 0.02 mg kg−1 in naans. The concentrations of KBrO3 in bread, cake, burger buns, pizza, and naans surpass the recommended threshold established by the FDA factors of 276.5, 309.0, 84.5, 217.5, and 268.5, respectively. The study revealed particularly high levels of KBrO3 presence in the targeted baked foods in all of the sampling districts, highlighting a serious food safety concern in Bangladesh.