Employing a new approach toward thermodynamic phase space, we investigate the phase transition, critical behavior and microscopic structure of higher dimensional black holes in an Anti-de Sitter (AdS) background and in the presence of Power-Maxwell field. In contrast to the usual extended $P-V$ phase space where the cosmological constant (pressure) is treated as a thermodynamic variable, we fix the cosmological constant and treat the charge of the black hole (or more precisely $Q^s$) as a thermodynamic variable. Based on this new standpoint, we develop the resemblance between higher dimensional nonlinear black hole and Van der Waals liquid-gas system. We write down the equation of state as $% Q^s=Q^s(T,\psi)$, where $\psi$ is the conjugate of $Q^s$, and construct a Smarr relation based on this new phase space as $M=M(S,P,Q^s)$, while $% s=2p/(2p-1)$ and $p$ is the power parameter of the Power-Maxwell Lagrangian. We obtain the Gibbs free energy of the system and find a swallowtail behaviour in Gibbs diagrams, which is a characteristic of first-order phase transition and express the analogy between our system and van der Waals fluid-gas system. Moreover, we calculate the critical exponents and show that they are independent of the model parameters and are the same as those of Van der Waals system which is predicted by the mean field theory. Finally , we successfully explain the microscopic behavior of the black hole by using thermodynamic geometry. We observe a gap in the scalar curvature $R$ occurs between small and large black hole. The maximum amount of the gap increases as the number of dimensions increases. We finally find that character of the interaction among the internal constituents of the black hole thermodynamic system is intrinsically a strong repulsive interaction.