It refers to the process of selection, where one atom is selected over other atoms by some specific reagent.
It determines which chemical product from that specific reaction is the major product and which is the minor product in a chemical process with many products.
This is reliant on the reagent molecules' likely attachment sites to the target molecule.
For example
The concept of regioselectivity is explained in Markovnikov’s rule, where two products are produced, in which the major product is formed due to the stable intermediate.
The reaction of Hydrogen bromide and propene gives two products a major (2-bromopropane) and a minor (1-bromopropane), which are called regioisomers.