According to the Bible, yes, Eve was Adam’s only wife. There is no other reference to Adam having an intimate relationship with another woman than Eve, the woman formed from his rib (Genesis 2:18:23).
Many centuries after the Bible was written and compiled, a Jewish legend grew up about a woman named Lilith who was said to have been Adam’s first wife, created from the same ground and at the same time as Adam. In the Middle Ages this legend was greatly developed, especially the notion that Lilith left Adam and the Garden of Eden when she refused to be subservient to her husband. Sometimes today this Lilith figure still shows up in cultic and literary references.