This article presents a novel methodology dedicated to retrieving the optical and microphysical properties of ice and liquid water clouds simultaneously. An optimal estimation method is used to retrieve the ice water path of one ice‐cloud layer and the optical thickness and droplet effective radius of up to two liquid‐water cloud layers, along with rigorous uncertainties. In order to perform the retrievals, radiometric measurements in five channels ranging from the visible to the thermal infrared are utilized. The position of cloud layers is currently provided by lidar information, which narrows the retrievals to its track. In the first part of this article, theoretical information content analyses are performed under different atmospheric conditions, over an oceanic surface. This type of analysis quantifies prior to the retrievals the amount of information that should be available regarding each parameter to be retrieved and helps to identify which set of channels provides this information. It is observed that strong information can be expected for retrieving each parameter in double‐layer cases, while yet stronger limitations appear in triple‐layer cases. In the second part of this article, our methodology is applied to a case study. In agreement with a priori expectations, accurate retrievals of ice and liquid cloud properties are obtained. These results are later compared with the products of a single‐layer retrieval method, Cloud‐Aerosol Lidar with Orthogonal Polarization (CALIOP) operational products and in situ estimates. We show that a much better consistency with the latter two is found when retrieving the properties of each layer simultaneously. However, further statistical analyses and comparisons with various operational products should be undertaken for validation of the methodology. Such results will be presented in the second part of this study.