Introduction: Thoracic kyphosis commonly occurs in subacromial impingement syndrome. This pilot study investigated the effect of thoracic joint mobilization and extension exercise on improving thoracic alignment and shoulder function. Methods: In total, 30 patients with subacromial impingement syndrome were recruited and randomly assigned to three groups, the joint mobilization group (n = 10), exercise group (n = 10), and combination group (n = 10). After four weeks of treatment, the measured outcomes included thoracic kyphosis using a manual inclinometer; pectoralis major (PM) and upper trapezius (UT) muscle tone and stiffness using the MyotonPRO®; affected side passive range of motion (ROM) using the goniometer (flexion, abduction, medial rotation, and lateral rotation); and shoulder pain and disability index (SPADI). Results: All three groups had significant improvements in all variables (p < 0.05). Thoracic kyphosis; UT muscle tone; and flexion, medial rotation, and lateral rotation ROM and SPADI were all significantly improved in the combination group compared to the mobilization and exercise groups (p < 0.05). Conclusions: The combination therapy of thoracic mobilization and extension exercise can be regarded as a promising method to improve thoracic alignment and shoulder function in patients with subacromial impingement syndrome.