My boyfriend coughe up blood in the mornings could this be caused from him smoking?

Yes... Coughing up blood is called hemoptysis and it is a serious symptom that always requires a medical evaluation. He may have bronchitis, either acute or chronic, but malignancy needs to be ruled out. If he continues to smoke, his airways will remain inflamed and worsen his symptoms. His doctor can also help w/smoking cessation.
Pulmonologist. Must see pulmonologist to obtain a flexible bronchoscopy and cat scan thorax with and without contrast. Need to evaluate to try to rule out cancer as the cause of hemoptysis. Hemoptysis is the term for coughing up blood.
See doctor. Coughing up blood needs evaluation by a doctor. Could be from infection, blood clot, cancer, or other things.