This paper presents a novel unscented Kalman filter (UKF) implementation with adaptive covariance matrices (ACMs), to accurately estimate the longitudinal and lateral components of vehicle velocity, and thus the sideslip angle, tire slip angles, and tire slip ratios, also in extreme driving conditions, including tyre–road friction variations. The adaptation strategies are implemented on both the process noise and measurement noise covariances. The resulting UKF ACM is compared against a well-tuned baseline UKF with fixed covariances. Experimental test results in high tyre–road friction conditions show the good performance of both filters, with only a very marginal benefit of the ACM version. However, the simulated extreme tests in variable and low-friction conditions highlight the superior performance and robustness provided by the adaptation mechanism.