It seems like a very niche case, where a matrix must be Hermitian positive semi-definite. In the case of reals, it simply must be symmetric.
How often does one have a positive semi-definite matrix in which taking it's Cholesky Decomposition has a significant usage?
Symmetric and positive definite matrices that can be Cholesky factored appears in many applications:
As to why one would use the Cholesky factorization rather than another matrix factorization such as the LU factorization, the answer is that Cholesky factorization is substantially faster than LU factorization because it can exploit the symmetry of the matrix and because pivoting isn't required. Cholesky factorization of sparse positive definite matrices is fairly simple in comparison with LU factorization because of the need to do pivoting in LU factorization.