A set-theoretic solution to the Pentagon Equation can be described as a pentagon algebra \((S, \cdot , *)\) such that \((S, \cdot )\) is a semigroup and the operations \(\cdot \) and \(*\) are related by two additional equations. This paper aims to investigate associative pentagon algebras in which \((S, *)\) is also a semigroup. We introduce and describe two families of associative pentagon algebras which are strongly determined by the properties of the semigroup \((S,*)\) . We present a complete characterization of such algebras using semigroup equations. We also provide constructions of such associative pentagon algebras and give several classes of examples.