Transition metal dichalcogenide MoS2 is a two-dimensional material, attracting much attention for next-generation applications thanks to rich functionalities stemming from its crystal structure. Many experimental and theoretical works have focused on the spin-orbit interaction which couples the valley and spin degrees of freedom so that the spin-states can be electrically controllable. However, the spin-states of charge carriers and atomic vacancies in devices have not been yet elucidated directly from a microscopic viewpoint. Here, we report the spin-states in thin-film transistors using operando electron spin resonance spectroscopy. We have observed clearly different electron spin resonance signals of the conduction electrons and atomic vacancies, and distinguished the corresponding spin-states from the signals and theoretical calculations, evaluating the gate-voltage dependence and the spin-susceptibility and g-factor temperature dependence. This analysis gives deep insight into the MoS2 magnetism and clearly indicates different spin-scattering mechanisms compared to graphene, which will be useful for improvements of the device characteristics and new applications.