The complexes of $C_2-;and;C_6$-dihydroceramides with transition metal ions have been investigated by using Electrospray ionization-tandem mass spectrometry (ESI-MS/MS). The formation and fragmentation pathways of several doubly charged cluster ions as well as singly charged cluster ions of $C_2-;and;C_6$-dihydroceramides with transition metal ions have studied by ESI-MS/MS in the positive mode. Under ESI conditions, dihydroceramides form singly and doubly charged complexes with transition metal ions $(Mn^{2+},;Fe^{2+},;Co^{2+},;Ni^{2+},;and;Zn^{2+};except;Cu^{2+})$ with the compositions of $[DHCer+M+2H^2O-H]^+,;[2DHCer+M+2H2O-H]^+,;[3DHCer+M+2H2O-H]^+,;[2DHCer+M]^{2+},;[3DHCer+M]^{2+},;[4DHCer+M]^{2+},;[5DHCer+M]^{2+},;and;[6DHCer+M]^{2+};(DHCer;=;C_2-;or;C_6$-dihydroceramide, M = transition metal ion). The different complexation behavior of copper is responsible for relatively lower affinity of dihydroceramides to copper compared to those of other transition metals. It is also found that in the mass spectrum of the dihydroceramide complexes with copper(II), [2DHCer+Cu-H]$^+$ was observed with considerable intensity as well as [2DHCer+Cu+2$H_2O-H]^+$ due to its different geometry from those of other metals.