We characterize Fredholm determinants of a class of Hankel composition operators via matrixvalued Riemann-Hilbert problems, for additive and multiplicative compositions. The scalar-valued kernels of the underlying integral operators are not assumed to display the integrable structure known from the seminal work of Its, Izergin, Korepin and Slavnov [41]. Yet we are able to describe the corresponding Fredholm determinants through a naturally associated Riemann-Hilbert problem of Zakharov-Shabat type by solely exploiting the kernels' Hankel composition structures. We showcase the efficiency of this approach through a series of examples, we then compute several rank one perturbed determinants in terms of Riemann-Hilbert data and finally derive Akhiezer-Kac asymptotic theorems for suitable kernel classes.