According to all the consensus and statements of the major societies, hypogonadism should be considered a medical problem, termed late onset hypogonadism (LOH) or testosterone deficiency syndrome (TDS), only when symptoms are present. One of the most common symptoms of LOH/TDS is sexual dysfunction (SD). The main purpose of this review is to discuss the role of testosterone (T) in men's sexual function, including epidemiology, pathophysiology, diagnostic procedures, and treatment efficacy in patients affected by erectile dysfunction (ED). The prevalence of hypogonadism in men with ED ranges from 1.7% to 35%. In ED patients, hypogonadism is often associated with reduced sexual desire and nocturnal penile erections, while association with sex-induced erection is less evident. This is because T regulates not only cyclic guanosine monophosphate (cGMP) formation, through nitric oxide synthase (NOS) stimulation, but also its catabolism, through phosphodiesterase-5 (PDE5) activity. The androgen-dependent PDE5 expression could explain the reduced effectiveness of PDE5 inhibitors (PDE5i) in the treatment of erectile dysfunction in hypogonadal patients. Accordingly, T substitution in these subjects restores responsiveness to PDE5i. Recognising hypogonadism in patients with ED is essential in order to appropriately treat the disease. However, suspecting LOH/TDS in SD patients is not an easy task. Recently published structured inventories, such as ANDROTEST, might help physicians to recognize hypogonadism and to further pursue its appropriate diagnosis and treatment.