Why Spontaneous Polarization in III-V Nitrides?III-V nitrides and their alloys represent a very special class of Materials. They are best chosen for UV-blue light-emitting devices because of their favorable mechanical properties and the wide and direct band gap. At the same time, among III-V semiconductors, III-V nitrides, (III-Ns hereafter), are the only ones that show a property called spontaneous polarization (P sp ), a builtin electric polarization absent in other well-known semiconductors used in optoelectronic devices such as GaAs and ZnSe. This property is of importance in applications since it tends to spoil the quantum efficiency of optoelectronic devices based on multi-quantum wells (MQWs) nanostructures. Also, P sp prediction and control is part of the technological development of electronic devices like AlGaN/GaN High Electron Mobility Transistors (HEMT's). In nature there exist two types of materials carrying a P sp : the ferroelectrics and the pyroelectrics. In ferroelectrics the P sp can be inverted by applying a suitably strong electrostatic field. This effect, known as bistability, is very important since it allows an accurate measurement of the P sp . In pyroelectrics P sp cannot be directly measured because its direction and orientation cannot be altered and is always parallel to a low symmetry axis of the crystal, this being called the pyroelectric axis. Luckily, just after GaN became a target of technological applications, a big step forward in the theory of solids, called the Modern Theory of Polarization (MTP) [1], sometimes referred to as Berry's phase method, provided an easy and accurate way to compute P sp for the first time. Within MTP the calculation of P sp is performed using first-principles computational tools and does not require a previous experimental knowledge about the material structure.Among the tetrahedrally coordinated solids, the most common pyroelectrics have a wurtzite structure; thus we find AlN, GaN, InN (the subject of this work), the hexagonal polytypes of SiC and well-known II-VI semiconductors such as ZnO and BeO [2]. In wurtzite crystals the pyroelectric axis is parallel to the [0001] direction and P sp will be equally oriented. In pyro-