Abstract. Pseudo-multiplicative unitaries on C*-modules generalize the multiplicative unitaries of Baaj and Skandalis [1], and are analogues of the pseudo-multiplicative unitaries on Hilbert spaces studied by Enock, Lesieur, Vallin [5], [10], [21]. We introduce Hopf C*-families on C*-bimodules and associate to special classes of pseudo-multiplicative unitaries two Hopf C*-families. Furthermore, we discuss dual pairings and counits on these Hopf C*-families, étalé and proper pseudo-multiplicative unitaries, and two classes of examples. In a later article, we will study regularity conditions on pseudo-multiplicative unitaries, coactions of Hopf C*-families on C*-algebras, and duality.Mathematics Subject Classification (2000). 46L55; 46L08, 22A22, 46L05.