Markonikov's Rule:

"when an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl halide, the
hydrogen adds to the carbon of the alkene that has the greater number of hydrogen substituents,
and the halogen to the carbon of the alkene with the fewer number of hydrogen substituents"

This is illustrated by the following example:

Look at the position of the H and the Br in relation to the statement of Markovnikovs
rule given above. Note that the major product, which is often referred to as the
Markovnikov product, is the more highly substituted alkyl halide. In the example above,
the secondary bromide is formed in preference to the primary bromide.

 Modern mechanistic knowledge indicates reaction occurs via protonation of the alkene to
give the more stable carbocation intermediate:

Here we see that in principle, propene can protonate to give two different carbocations, one
2o and the other 1o.
Formation of the more stable 2o carbocation is preferred.

 The carbocation then reacts with the nucleophile (e.g. the halide ion) to give the alkyl
bromide and hence 2-bromopropane is the major product.

Although Markovnikov's rule was developed for and is specifically applied to the addition of
hydrogen halides to alkenes, many other additions are also described as Markovnikov or anti-
Markovnikov depending on the regioselectivity of the addition reaction, e.g. the acid catalysed
hydration of alkenes (Markovnikov).
In more general terms, Markovnikov's rule can be "modernised" to cover other addition reactions
by considering that the electrophile adds to the least substituted end of the alkene giving rise to
the more stable intermediate. So let's rephrase our statement of Markovnikov's rule:

"when an unsymmetrical alkene undergoes addition with E-Nu, then the electrophile, E, adds to
the carbon of the alkene that has the greater number of hydrogen substituents, and
the nucleophile, Nu, to the carbon of the alkene with the fewer number of hydrogen substituents"

Therefore, the key is to recognise the electrophilic portion of the reagent as it adds to the π bond
first so as to give the more stable intermediate.