Speaking about pain, we use the verb doler. It works like gustar: first, we indicate who has pain with a dative of personal pronoun (me, te, le, nos, os, les), then we put duele if the organ where we feel pain is in Singular, and duelen when it is in Plural, finally, we mention the part of the body that makes pain:
me/te/le/nos/os/les + DUELE / DUELEN + parte del cuerpo
The same is true for the verb picar (to itch):
Me duelen los brazos – My arms hurt
Le pica la cabeza – His head itches
Remember to agree in number:
Me duele_ la cabeza
Me duelen los pies
Please, note that we never use posessive pronouns with organs that hurt, we must use definite article instead:
INCORRECTO: *Le duelesucorazón
CORRECTO: Le duele el corazón
The person who feels pain must be indicated with a Dative form of personal pronouns (me, te, le...). If we mention her explicitly, we must use the construction a + persona + le/les:
A Carlos le duele la garganta
– Carlos has a sore throat
A Ana y Javier les duele la tripa – Ana and Javier hurt their gut