Hello,
Yes, every symmetric, positive semi-definite matrix is the covariance matrix of some multivariate distribution. To prove this fact, it suffices to give an example. Let Σ be an nxn positive semi-definite matrix, and let μ be any n-dimensional real vector. Then we can simply take the (n-dimensional) multivariate normal distribution with mean μ and covariance matrix Σ as the desired example. [If an n-dimensional random vector X has the multivariate normal distribution mentioned here, we often designate this by X∼N(μ,Σ).]
Hope that helps,
William