Among chemical components present in both green and roasted coffee, bioactive amines play important roles in coffee quality and safety and in human health. From a health standpoint, serotonin and melatonin are neuroactive and exert antioxidant activity in vitro and in vivo, despite the small concentrations found in coffee beverage. The polyamines spermidine and spermine are efficient free radical scavengers in a number of chemical and enzymatic systems. Agmatine, which can be formed during roasting, has been reported to exert modulatory action in multiple molecular targets, such as neurotransmitter and nitric oxide (NO) synthesis and polyamine metabolism. These amines could possibly contribute to many of the beneficial effects to human health associated with moderate coffee intake. These aspects will be approached in the present chapter.