Compared to pyrolytic graphite (PG) and pyrolytically coated polycrystalline graphite (PCPG), which are commonly employed substrates for graphite furnace atomic absorption spectrometry (GFAAS), highly oriented pyrolytic graphite (HOPG) is characterized by a high degree of c-axis alignment with relatively few active sites and imperfections present on the surface. The usefulness of HOPG and commercial PG platforms for the determination of lead, copper, and aluminum by GFAAS was compared. Qualitative comparison of the absorption profiles and temperature optimizations suggest that lead, copper with a chemical modifier (palladium), and aluminum interact similarly with the two graphite substrates, while copper without a modifier interacts less strongly with HOPG than with PG. These results are in agreement with previous studies that have demonstrated that copper interacts strongly with PG and PCPG. HOPG and PG were employed for the determination of a pine needles standard reference material (SRM) and Fraser fir (Abies fraseri) samples. The analyses of the SRM gave good agreement with the certified value using both substrates, and comparable values were obtained for the samples. These results suggest that HOPG may be useful as a model for PG or PCPG when techniques such as scanning tunneling microscopy that require a high degree of c-axis alignment are employed.