Final answer:
Leuprolide is the most suitable initial pharmacological treatment for a patient with rising PSA levels post-prostatectomy for prostate cancer, as it helps suppress testosterone that fuels cancer cell growth.
Step-by-step explanation:
The most appropriate initial pharmacological agent for a 67-year-old man presenting with an elevated serum prostate specific antigen (PSA) after a prostatectomy would be Leuprolide (option B). Leuprolide is a type of hormone therapy that suppresses the production of testosterone, which can help in controlling the growth of prostate cancer cells. Other listed options like Doxazosin, Tadalafil, and Terazosin are not typically used for the treatment of prostate cancer but may be used to manage symptoms associated with benign prostatic hyperplasia (BPH) or erectile dysfunction.