This study outlines a simple fluorometric optical sensor system for the sensitive, real time measurement of volatile organic compounds (VOCs) as biomarkers of urinary bladder cancer in patients presenting with frank hematuria and confirmed to have the disease on histopathology. Arrays of 24 sensor points based on fluorescence VOC sensitive materials were made. Urine samples of 38 consecutive patients with pathologically confirmed bladder tumours and 41 age and gender matched healthy controls were recruited and analysed using this sensor array. This system correctly classified 68 out of 79 urine samples with 84.21% sensitivity and 87.80% specificity; the system also achieved 66.67% sensitivity and 75.00% specificity for classification of high-grade and low-grade bladder cancer patients. This study showed promising results in the detection of urinary bladder cancer as well as to classify high grade versus low grade bladder cancers.