In this study, a novel step climbing method for a five-wheeled wheelchair, composed of a manual wheelchair and an active-caster drive system, has been proposed. Because the active-caster has the same configuration as a passive caster, an arbitrary velocity can be generated by controlling its wheel and steering shafts. Thus, the motion of the proposed wheelchair can be controlled in 2DOF (two degrees of freedom) despite the single-wheel drive system. Moreover, by changing the number of points of contact between the wheelchair and the ground using a linear actuator, two types of motion can be accomplished, similar to front and rear drive modes. In addition, a novel add-on mechanism, which can perform not only the suggested step climbing method but also the previous functions of the wheelchair, has been proposed. Because the five-wheeled wheelchair has five points of contact with the ground, when the front casters hover above the ground, the wheelchair has adequate stability due to other three wheels contacting the ground to easily perform a "static wheelie" motion. Similarly, the wheelchair can also maintain its stability when the large wheels hover above the ground. The proposed method makes use of this stability to achieve the step climbing of the front casters and large wheels, whereas the drive wheel is lifted onto the step by cooperative control of the linear actuator and drive wheel. By comparing with a step climbing method that uses only the traction force of the drive wheel, the advantages of the proposed method were analyzed. Moreover, the design conditions of the proposed mechanism for realizing the suggested step climbing method were derived. Finally, a prototype was built and experimentally tested to confirm that the wheelchair user can climb over a step using the proposed method and mechanism.