The Combined matrix of a nonsingular matrix A is defined by φ (A) = A • A −1 T where • means the Hadamard (entrywise) product. If the matrix A describes the relation between inputs and outputs in a multivariable process control, φ (A) describes the "relative gain array" (RGA) of the process and it defines the Bristol method [1] often used for Chemical processes [13, 15, 16]and [11, 8]. The combined matrix has been studied in several works such as [3], [6] and [10]. Since φ (A) = (c i j) has the property of ∑ k c ik = ∑ k c k j = 1, ∀i, j, when φ (A) ≥ 0, φ (A) is a doubly stochastic matrix. In certain chemical engineering applications a diagonal of the RGA in wchich the entries are near 1 is used to determine the pairing of inputs and outputs for further design analysis. Applications of these matrices can be found in Communication Theory, related with the satellite-switched time division multipleaccess systems, and about a doubly stochastic automorphism of a graph. In this paper we present new algorithms to generate doubly stochastic matrices with the Combined matrix using Hessenberg matrices in section 3 and orthogonal/unitary matrices in section 4. In addition, we discuss what kind of doubly stochastic matrices are obtained with our algorithms and the possibility of generating a particular doubly stochastic matrix by the map φ .