ABSTRACTPure component decomposition problems in chemometrics can be classified into rankâregular and rankâdeficient problems. Rankâdeficient problems are characterized by a spectral data matrix that has a lower rank than the number of chemical species. However, it is possible that there exists rankâregular factorization of the spectral data matrix, but none of these solutions can be interpreted chemically, and only a solution of the MCR problem with rank deficiency is chemically meaningful. Then we say that the underlying problem suffers from a hidden rank deficiency. In this paper, MCR problems with hidden rank deficiency are introduced and analyzed with several examples for problems of rank 2 and rank 3. The area of feasible solutions is determined with the help of additional constraints on the solution.