A two-dimensional, single-phase, isothermal, multicomponent, transient model is built to investigate the transport phenomena in unitized regenerative fuel cells (URFCs) under the condition of switching from the fuel cell (FC) mode to the water electrolysis (WE) mode. The model is coupled with an electrochemical reaction. The proton exchange membrane (PEM) is selected as the solid electrolyte of the URFC. The work is motivated by the need to elucidate the complex mass transfer and electrochemical process under operation mode switching in order to improve the performance of PEM URFC. A set of governing equations, including conservation of mass, momentum, species, and charge, are considered. These equations are solved by the finite element method. The simulation results indicate the distributions of hydrogen, oxygen, water mass fraction, and electrolyte potential response to the transient phenomena via saltation under operation mode switching. The hydrogen mass fraction gradients are smaller than the oxygen mass fraction gradients. The average mass fractions of the reactants (oxygen and hydrogen) and product (water) exhibit evident differences between each layer in the steady state of the FC mode. By contrast, the average mass fractions of the reactant (water) and products (oxygen and hydrogen) exhibit only slight differences between each layer in the steady state of the WE mode. Under either the FC mode or the WE mode, the duration of the transient state is only approximately 0.2 s.