Cayley Commutator-free Methods for Krotov-Type Algorithms in Quantum Optimal Control This paper presents a class of structure-preserving numerical methods for quantum optimal control problems, based on commutator-free Cayley integrators. Starting from the Krotov framework, we reformulate the forward and backward propagation steps using Cayley-type schemes that preserve unitarity and symmetry at the discrete level. This approach eliminates the need for matrix exponentials and commutators, leading to significant computational savings while maintaining higher-order accuracy. We first recall the standard linear setting and then extend the formulation to nonlinear Schrödinger and Gross-Pitaevskii equations using a Cayley-polynomial interpolation strategy. Numerical experiments on state-transfer problems illustrate that the CF-Cayley method achieves the same accuracy as high-order exponential or Cayley-Magnus schemes at substantially lower cost, especially for longtime or highly oscillatory dynamics. In the nonlinear regime, the structure-preserving properties of the method ensure stability and norm conservation, making it a robust tool for large-scale quantum control simulations. The proposed framework thus bridges geometric integration and optimal control, offering an efficient and reliable alternative to existing exponential-based propagators.