Markovnikov's Rule states that when HX is added to an alkene, the proton (H) will add to the carbon atom of the double bond that has the greater number of hydrogen atoms (the more substituted carbon), and the halide (X) will add to the carbon with fewer hydrogen atoms.
This rule explains the regioselectivity of the reaction, as the more stable carbocation intermediate is formed faster, leading to the observed product distribution.
Thus, the correct answer is (a) Markovnikov's Rule.