This study aimed to assess the association between smartphone use in the sitting posture and changes in thoracolumbar kyphosis, lumbar lordosis, and pelvic asymmetry in adolescents with low back pain (LBP). Twenty-five adolescents with LBP and 25 healthy adolescents participated in this study. They were instructed to sit on a height-adjustable chair with their hips and knees bent at 90° for 30 min in their usual sitting postures. Thoracolumbar kyphosis, lumbar lordosis, and pelvic asymmetry were measured using a three-dimensional motion capture system. Thoracolumbar kyphosis and lumbar lordosis increased after 30 min of sitting compared to the baseline. In both groups, thoracic kyphosis and lumbar lordosis angle increased with increasing sitting time. Compared to healthy adolescents, adolescents with LBP presented greater thoracolumbar kyphosis and lumbar lordosis after prolonged sitting. Pelvic asymmetry showed no significant difference between the sitting time and groups. Using a smartphone during prolonged sitting may lead to a slumped posture; these associations were more pronounced in adolescents with LBP.