We investigate the internal structure of the ground (1S) and the first two radially excited (2S, 3S) states of the pion within the light-front quark model. The valence Fock sector is described using pure harmonic-oscillator eigenstates and mixed states formed as orthogonal linear combinations of these eigenfunctions. The optimal wavefunction parameters are determined through a variational procedure based on a QCD-motivated effective Hamiltonian. Using the resulting light-front wavefunctions, we study the pion distribution amplitude, parton distribution function, and electromagnetic form factor. After QCD evolution, the ground state distribution amplitude and parton distribution function are found to be in good agreement with available experimental data. At the model scale, the parton distribution functions of the 1S and 2S states show clear sensitivity to state mixing, while the distribution amplitudes and electromagnetic form factors are weakly sensitive. In contrast, for the 3S state, all three observables exhibit a pronounced sensitivity to mixing. The decay constants of the mixed states are also found to decrease sequentially with increasing radial excitation.