Geostatistical regression models are widely used in environmental and geophysical sciences to characterize the mean and dependence structures for spatio-temporal data. Traditionally, these models account for covariates solely in the mean structure, neglecting their potential impact on the spatio-temporal covariance structure. This paper addresses a significant gap in the literature by proposing a novel covariate-dependent covariance model within the spatio-temporal random-effects model framework. Our approach integrates covariates into the covariance function through a Cholesky-type decomposition, ensuring compliance with the positive-definite condition. We employ maximum likelihood for parameter estimation, complemented by an efficient expectation conditional maximization algorithm. Simulation studies demonstrate the superior performance of our method compared to conventional techniques that ignore covariates in spatial covariances. We further apply our model to a PM2.5 dataset from Taiwan, highlighting wind speed’s pivotal role in influencing the spatio-temporal covariance structure. Additionally, we incorporate wind speed and sunshine duration into the covariance function for analyzing Taiwan ozone data, revealing a more intricate relationship between covariance and these meteorological variables.