Polarization encoding has been extensively used in quantum key distribution (QKD) implementations along free-space links. However, the calculation model to characterize channel transmittance and quantum bit error rate (QBER) for free-space QKD has not been systematically studied. As a result, it is often assumed that misalignment error is equal to a fixed value, which is not theoretically rigorous. In this paper, we investigate the depolarization and rotation of the signal beams resulting from spatially-dependent polarization effects of the use of curved optics in an off-axis configuration, where decoherence can be characterized by the Huygens–Fresnel principle and the cross-spectral density matrix (CSDM). The transmittance and misalignment error in a practical free-space QKD can thus be estimated using the method. Furthermore, the numerical simulations clearly show that the polarization effect caused by turbulence can be effectively mitigated when maintaining good beam coherence properties.