We consider the orthogonalisation of the signature of a stochastic process as the analogue of orthogonal polynomials on path-space. Under an infinite radius of convergence assumption, we prove density of linear functions on the signature in $L^p$ functions on grouplike elements, making it possible to represent a square-integrable function on (rough) paths as an $L^2$-convergent series. By viewing the shuffle algebra as commutative polynomials on the free Lie algebra, we revisit much of the theory of classical orthogonal polynomials in several variables, such as the recurrence relation and Favard's theorem. Finally, we restrict our attention to the case of Brownian motion with and without drift, and prove that dimension-independent orthogonal signature exists with drift but not without. We end with numerical examples of how orthogonal signature polynomials of Brownian motion can be applied for the approximation of functions on paths sampled from the Wiener measure.