This study presents a misalignment light-guiding module to increase the effectiveness of absorbing light. For a general fixed-type photovoltaic (PV) panel, the misalignment light decreases the efficiency of the system. A solar tracking system was installed for obtaining higher power generation. However, the cost of the PV system and maintenance was 5−10 times higher than the general type. In this study, this module is composed of an array of misalignment light-guiding units that consist of a non-axisymmetric compound parabolic curve (NACPC) and a freeform surface collimator. The NACPC efficiently collects the misalignment light within ±30° and guides the light to the collimator. The light has a better uniformity and smaller angle at the exit aperture. The simulation results show that the optical efficiency of the unit was above 70% when the misalignment angle was smaller than 20°. The experimental results show that the power generation of the light-guiding unit was 1.8 times higher than the naked PV panel.