Axillary web syndrome (AWS) occurs after breast cancer surgery, sentinel lymph node dissection, or sentinel lymph node biopsy. Here, cord-like structures from the axilla to the forearm limit the range of motion of the shoulder joint and cause pain. Although the etiology is unknown, AWS has been attributed to the blockage of normal lymphatic flow. Here, we report a novel case of AWS after venous blood sampling in a patient. A healthy, 31-year-old male patient experienced pain with a limited range of motion of the shoulder joint the day after venous blood was collected from the left upper extremity for a medical checkup, and he presented to an orthopedic outpatient clinic on the day. Palpation of the axillary region disclosed a cord-like structure in the axillary region of the shoulder joint during abduction, and the patient was diagnosed with AWS. The cord-like structure was noted to be a hypoechogenic luminal structure on ultrasound (US) examination of the axilla, extending from the axilla to below the ulnar cutaneous vein from which the blood was drawn. In patients with pain and a limited range of motion of the shoulder joint, only the shoulder joint is examined during an orthopedic examination. It is important to obtain appropriate physical findings for possible AWS.