A model to core-shell structured polymer nanofibers deposited via coaxial electrospinning is presented. Investigations are based on a modified Jacobi-Gauss collocation spectral method, proposed along with the Boubaker Polynomials Expansion Scheme (BPES), for providing solution to a nonlinear Lane-Emden-type equation. The spatial approximation has been based on shifted Jacobi polynomials P (α,β) T,N (x) with α, β(−1, ∞), T > 0 was n the polynomial degree. The Boubaker Polynomials Expansion Scheme (BPES) main features, concerning the embedded boundary conditions, have been outlined. The modified Jacobi-Gauss points are used as collocation nodes. Numerical examples are included to demonstrate the validity and applicability of the technique, and a comparison is made with existing results. It has been revealed that both methods are easy to implement and yield very accurate results.