For the passive intermodulation (PIM) problem of nonlinear contact on microwave connectors, an effective method is presented to improve the computational accuracy of PIM. First of all, the contact stress distribution on contact surface is analyzed by finite-element method based on the Weierstrass–Mandelbrot model. The contact stress and real area of contact are evaluated under different loading conditions. Then, the electrical parameters of physical effects of nonlinear contact are derived based on the electric contact theory and the physical effects of metal–metal microcontact. Finally, the nonlinear I–V relation is established from the microcontact equivalent circuit, and the third-order PIM power level generated by contact nonlinearity is revealed in analytic form. The analytic results are verified by the PIM test experiments. This work provides a novel way for PIM calculation of rough surface contact.