Recently, five-axis machining centers with non-orthogonal rotation axes have been developed to achieve a high stiffness and large machinable area. Although such machine tools can expand the manufacturing field, adopting not only orthogonal axes, but also non-orthogonal axes, requires generalization of conventional form-shaping theory. Moreover, since it is not possible to imagine simultaneous five-axis movement of machine tools with non-orthogonal axes, it is important to analyze the validity of the developed machine tools with non-orthogonal axes using generalized form-shaping theory by a structure analysis method. In the present paper, generalization of the form-shaping function is first performed, and the conditions whereby machining centers with non-orthogonal axes can achieve every position and posture are clarified for an index showing the validity of the machine tool structure. Finally, the machining feasibility is verified for a machine tool structure with non-orthogonal axes using the derived conditions.