Hollow organ perforation can precipitate a life-threatening emergency due to peritonitis followed by fulminant sepsis and fatal circulatory collapse. Pneumoperitoneum is typically detected as subphrenic free air on frontal chest X-ray images; however, treatment is reliant on accurate interpretation of radiographs in a timely manner. Unfortunately, it is not uncommon to have misdiagnoses made by emergency physicians who have insufficient experience or who are too busy and overloaded by multitasking. It is essential to develop an automated method for reviewing frontal chest X-ray images to alert emergency physicians in a timely manner about the life-threatening condition of hollow organ perforation that mandates an immediate second look. In this study, a deep learning-based approach making use of convolutional neural networks for the detection of subphrenic free air is proposed. A total of 667 chest X-ray images were collected at a local hospital, where 587 images (positive/negative: 267/400) were used for training and 80 images (40/40) for testing. This method achieved 0.875, 0.825, and 0.889 in sensitivity, specificity, and AUC score, respectively. It may provide a sensitive adjunctive screening tool to detect pneumoperitoneum on images read by emergency physicians who have insufficient clinical experience or who are too busy and overloaded by multitasking.