Financial institutions attach great importance to the multiple attribute decision-making (MADM) problems of selecting an effective third-party logistics (3PL) service provider in supply chain finance. A suitable 3PL service provider can not only assist financial institutions in carrying out supply chain finance activity but can also replace financial institutions in supervising the operation of a target financing supply chain, therefore minimizing financial institutions' operating risks. However, there is no sufficient study on the selection of a 3PL service provider. Hence, the objective of this paper is to establish an innovative concept of the “probabilistic complex hesitant fuzzy set” (PCHFS), which is a hybrid structure of the complex hesitant fuzzy set and the probabilistic fuzzy set to manage complex information in real-decision theory. This paper examines the periodicity of probabilistic fuzzy information and extends the range from [0, 1] to the unit disc in the complex plane to provide more ability to describe the full meaning of the information in a mathematical model. Based on the internal structure of the set and to find the degree of discrimination between the pairs of PCHFSs, the generalized distance measures and modified generalized distance measures are defined. Several properties and their relationships between them are derived in detail. Also, several cases of the proposed measures are exposed, which reduces them to the existing studies. Furthermore, based on these proposed measures, a multiple-attribute decision-making (MADM) approach is established in an uncertain environment, and several numerical examples are given to examine the feasibility and validity of the explored measures. Finally, the modified and parameterized distance measures based on PCHFSs are verified by comparing them with some existing measures.