Post-wall waveguide structures have attracted a great deal of attention for micro- and millimeter-wave applications. One of the waveguide’s applications is a slotted waveguide array. In order to design the slotted array, the characteristics of a slot unit alone on the post-wall waveguide should be investigated. In this paper, a method for extracting the S-parameters of a unit slot is proposed. This simple method requires only two kinds of waveguides: waveguides without a slot unit and waveguides with a slot unit. Three kinds of slot units are fabricated, and the extracted results show a high level of agreement with predicted (simulated) results. With this method, the equivalent slot length can also be found.