In this article, we propose a polarimetric calibration (PolCal) algorithm to estimate the system crosstalk, cross-polarization (x-pol), and co-polarization (co-pol) channel imbalance (CI) when ground corner reflectors (CRs) are unavailable. The current PolCal process requires at least one trihedral CR to determine the co-pol CI. However, the deployment of ground CRs is costly and may even be impossible in some areas. To calibrate a polarimetric image without CRs, our proposed method automatically extracts the volume-dominated and Bragg-like pixels as a reference to estimate the crosstalk, x-pol, and co-pol CI values. Then, a first-order polynomial model is exploited to fit the co-pol CI to further improve calibration accuracy. In the experimental section, we demonstrate the effectiveness of our proposed method with data from two of China’s newly developed very high-resolution systems. The experiments confirmed that the proposed workflow can be considered as a feasible calibration scheme when the ground deployment of CRs is impossible, and it is also an effective analysis tool for the assessment of calibrated products.