This paper first constructs a Milstein-type scheme for stochastic Volterra integral equations with doubly singular kernels. Then, we also study the Hölder continuity of the solution to these equations and investigate the convergence rate of the Milstein scheme. More precisely, the mean-square convergence rate is min{1−α1−β1,1−2α2−2β2}, where α1,α2,β1,β2 are the singularity exponents of the equations. The difficulty in obtaining our convergence results is the lack of Itô formula for the equations. To get around this problem, we adopt the Taylor formula and then perform a complex analysis of the equations satisfied by the solution. Moreover, we apply the multilevel Monte Carlo technique based on the Euler scheme and the fast Euler scheme for the equations to reduce the computational complexity. More concretely, to achieve given desired accuracy O(ϵ), the multilevel Monte Carlo technique based on the Euler scheme and the fast Euler scheme decrease the computational cost of the standard Euler scheme from Oϵ−2−2α˜ to Oϵ−2α˜ and O(ϵ−1α˜|logϵ|3) when T≈1. Finally, some numerical experiments are given to demonstrate our theoretical results.