In this paper we give a concrete application of the spectral theory based on the notion of S-spectrum to fractional diffusion process. Precisely, we consider the Fourier law for the propagation of the heat in non homogeneous materials, that is the heat flow is given by the vector operator:where e ℓ , ℓ = 1, 2, 3 are orthogonal unit vectors in R 3 , a, b, c are given real valued functions that depend on the space variables x = (x1, x2, x3), and possibly also on time. Using the H ∞ -version of the S-functional calculus we have recently defined fractional powers of quaternionic operators, which contain, as a particular case, the vector operator T . Hence, we can define the non-local version T α , for α ∈ (0, 1), of the Fourier law defined by T . We will see in this paper how we have to interpret T α , when we introduce our new approach called: "The S-spectrum approach to fractional diffusion processes". This new method allows us to enlarge the class of fractional diffusion and fractional evolution problems that can be defined and studied using our spectral theory based on the S-spectrum for vector operators. This paper is devoted to researchers working in fractional diffusion and fractional evolution problems, partial differential equations and non commutative operator theory. Our theory applies not only to the heat diffusion process but also to Fick's law and more in general it allows to compute the fractional powers of vector operators that arise in different fields of science and technology.This can also be done for quaternionic sectorial operators (and in particular for sectorial vector operators) using the quaternionic version of the H ∞ -functional calculus. The study of the fractional powers of quaternionic and of vector operators started with the paper [16]. The H ∞ -functional calculus has been extended to the quaternionic setting in [6], following the original paper of McIntosh [37]. This calculus can be developed with less restrictions on the operator as in [34]. Recently,in [17], we have extended the H ∞ -functional calculus in its full generality following this approach. In the same paper, we also proved some non trivial results like the spectral mapping theorem in this setting and we used this functional calculus to define and study fractional powers of quaternionic linear sectorial operators and in particular vector operators. In our papers we have extended several classical results of fractional powers of operators in [9,33,35,36,37,41,42] to the quaternionic setting.This paper has two main goals. The first one is to define a new approach to fractional diffusion processes that is based on the spectral theory on the S-spectrum, that we will call: The S-spectrum approach to fractional diffusion problems. The second is to give a concrete application to fractional diffusion problems and fractional evolution when the operator T defined in (1.1) has commuting components. Our theory applies more in general to operators T with non commuting components (a(x)∂ x 1 , b(x)∂ x 2 , c(x)∂ x 3 ) but, for the sake o...