Alternatives to coffee
Wikipedia lists a few substitutes, some of which are fairly readily available. These may be based on roasted grains (like barleycup), chicory (though this is often combined with coffee), or both. 

There are several processes for decaffeinating coffee. Not all rely on the organic solvents you're trying to avoid. The Swiss water process avoids then completely and is used commercially so you should be able to order some. CO2 decaffeinated coffee is rarer.