The mass and heat transfer mechanisms during radio frequency/vacuum (RF/V) drying of square-edged timber were analyzed and discussed in detail. Based on the mass and heat transfer theory of porous materials, a one-dimensional mathematical model was developed from conservation equations. Compared with conventional models, it has the following advantages: (1) Each independent variable has a separate governing equation and is solved independently by converting the partial differential equation into a difference equation with the finite volume method; and (2) The calculated data from different parts of the wood specimen are displayed in the evolution curves because the specimen is divided into several units along fiber direction. Therefore, the change law of the parameters can be better described. The software Matlab, which has the advantages of fast calculation speed and high precision, was used for programming and calculations. In addition, the square-edged timber Sugi specimen was dried in a laboratory RF/V dryer, and the total average moisture content (MC) and local temperature were monitored as a function of time. By analyzing the calculated and experimental results, it can be concluded that most of the important phenomena observed during RF/V drying can be adequately described by this model.