River salinisation and alkalinisation have become one of the major environmental problems threatening the safety of global freshwater resources. With the accelerated climate change and aggravating anthropogenic influences, it is important to identify the trends and causes of river salinisation and alkalinisation so that better mitigation measures could be taken. This study has focused on the UK rivers because there has been insufficient investigation on this topic. To understand the salinisation and alkalinisation trends and causes of rivers in the UK over the past 20 years from a vertical (analysis of each river) and horizontal (comparison of all rivers) perspective, this study uses the Theil-Sen regression and Mann-Kendall test to deal with the trends of conductivity (proxy on salinisation) and pH (proxy on alkalinisation), obtains outliers of conductivity and pH by boxplot, and calculates the Pearson’s and the Kendall’s Tau correlation coefficients (α = 0.05) between the water quality data and the potential factors (potential road salting, normalized difference vegetation index (NDVI), river discharge, agricultural and urban lands). The results show that the UK rivers are becoming more alkaline with a median pH increase of 0.05 to 0.40, but less salty with a median conductivity decrease of 0.06 to 0.11 mS/cm. And the changes in conductivity and pH have seasonality and regionality, which shows that there are usually greater changes in trends and medians of them in winter or through reaches with more anthropogenic disturbance. Furthermore, from a vertical perspective, the conductivity of more than 50% of rivers in this study is negatively correlated with NDVI and river discharge, and positively correlated with potential road salting, and the pH of that is positively correlated with agricultural lands. While from a horizontal perspective, NDVI and agricultural lands are positively correlated with pH, and potential road salting and urban lands are positively correlated with conductivity. Therefore, road salting, urbanisation, agricultural lands, river discharge and vegetation cover can be considered to affect river salinisation and alkalinisation in the UK.