We present a high-statistics lattice QCD determination of the valence parton distribution function (PDF) of pion, with a mass of 300 MeV, using two very fine lattice spacings of a = 0.06 fm and 0.04 fm. We reconstruct the x-dependent PDF, as well as infer the first few even moments of the PDF using the 1-loop perturbative LaMET framework. Our analyses use both RI-MOM and ratio-based schemes to renormalize the equal-time bi-local quark-bilinear matrix elements of pions boosted up to 2.4 GeV momenta. We use various model-independent and model-dependent analyses to infer the large-x behavior of the valence PDF. We also present technical studies on lattice spacing and higher-twist corrections present in the boosted pion matrix elements.