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In this paper, the maximum principle of variable-order fractional diffusion equations and the estimates of fractional derivatives with higher variable order are investigated. Firstly, we deduce the fractional derivative of a function of higher variable order at an arbitrary point. We also give an estimate of the error. Some important inequalities for fractional derivatives of variable order at arbitrary points and extreme points are presented. Then, the maximum principles of Riesz-Caputo fractional differential equations in terms of the multi-term space-time variable order are proved. Finally, under the initial-boundary value conditions, it is verified via the proposed principle that the solutions are unique, and their continuous dependance holds.