A thickness distribution model of photoresist spin-coating on concave spherical substrate (CSS) has been developed via both theoretical studies and experimental verification. The stress of photoresist on rotating CSS is analyzed and the boundary conditions of hydrodynamic equation are presented under the non-lubricating condition. Moreover, a multivariable polynomial equation of photoresist-layer thickness distribution is derived by analyzing and deducing the flow equation where the evaporation rate, substrate topography, interface slip between liquid and CSS, and the variation of rotational speed and photoresist parameters are considered in detail. Importantly, the photoresist-layer thickness at various CSS rotational speeds and liquid concentrations can be obtained according to the theoretical equation. The required photoresist viscosity and concentration parameters of different photoresist coating thickness under a certain coating speeds can be also solved through this equation. It is noted that the calculated theoretical values are well consistent with the experimental results which were measured with various CSS rotational speeds and liquid concentrations at steady state. Therefore, both our experimental results and theoretical analysis provide the guidance for photoresist dilution and pave the way for potential improvements and microfabrication applications in the future.