This volume features selected, refereed papers on various aspects of statistics, matrix theory and its applications to statistics, as well as related numerical linear algebra topics and numerical solution methods, which are relevant for problems arising in statistics and in big data. The contributions were originally presented at the 25th International Workshop on Matrices and Statistics (IWMS 2016), held in Funchal (Madeira), Portugal on June 6-9, 2016. The IWMS workshop series brings together statisticians, computer scientists, data scientists and mathematicians, helping them better understand each other’s tools, and fostering new collaborations at the interface of matrix theory and statistics.