Time-resolved photoluminescence (TRPL) and positron annihilation measurements, as well as Al0.23Ga0.77N/GaN heterostructure growth by metalorganic vapor phase epitaxy were carried out on very low defect density, polar c-plane and nonpolar m-plane freestanding GaN (FS-GaN) substrates grown by hydride vapor phase epitaxy. Room-temperature photoluminescence (PL) lifetime for the near-band-edge (NBE) excitonic emission of the FS-GaN substrates increases with increasing positron diffusion length (L+); i.e., decreasing gross concentration of charged and neutral point defects and complexes. The best undoped c-plane FS-GaN exhibits record-long L+ being 116 nm. The fast component of the PL lifetime for its NBE emission increases with temperature rise up to 100 K and levels off at approximately 1.1 ns. The result implies a saturation in thermal activation of nonradiative recombination centers. The surface and interface roughnesses for a Si-doped Al0.23Ga0.77N/GaN/Al0.18Ga0.82N/GaN heterostructure are improved by the use of FS-GaN substrates, in comparison with the structure fabricated on a standard GaN template. The emission signals related to the recombination of a two-dimensional electron gas and excited holes are recognized for an Al0.23Ga0.77N/GaN single heterostructure grown on the c-plane FS-GaN substrate.