The most common symptom of caffeine withdrawal is a headache, which often develops within 12 to 24 hours after the last ingestion of caffeine.The headache often develops slowly and is felt throughout the head. In some cases, the headache can become severe and throbbing.eadache. The most common symptom of caffeine withdrawal is a headache, which often develops within 12 to 24 hours after the last ingestion of caffeine. The headache often develops slowly and is felt throughout the head.