Complex q-rung orthopair fuzzy set (CQROFS) is a proficient technique to describe awkward and complicated information by the truth and falsity grades with a condition that the sum of the q-powers of the real part and imaginary part is in unit interval. Further, Schweizer–Sklar (SS) operations are more flexible to aggregate the information, and the Muirhead mean (MM) operator can examine the interrelationships among the attributes, and it is more proficient and more generalized than many aggregation operators to cope with awkward and inconsistence information in realistic decision issues. The objectives of this manuscript are to explore the SS operators based on CQROFS and to study their score function, accuracy function, and their relationships. Further, based on these operators, some MM operators based on PFS, called complex q-rung orthopair fuzzy MM (CQROFMM) operator, complex q-rung orthopair fuzzy weighted MM (CQROFWMM) operator, and their special cases are presented. Additionally, the multi-criteria decision making (MCDM) approach is developed by using the explored operators based on CQROFS. Finally, the advantages and comparative analysis are also discussed.