Parinari curatellifolia is the main species used to produce charcoal in Angola. Its chemical, anatomical, and thermal properties were analyzed. The bark is dark grey, rough, and corky, and the wood is brown to yellow-red. Compared to wood, bark fibers presented lower length, lumen, and wall thickness. There is not much difference between height and cell numbers of rays. Sieve tube elements appear solitary or in small groups (2–3 cells), and vessels were of two diameter classes but diffuse-porous. Bark basic density was lower than wood (505 kg.m− 3vs. 580 kg.m− 3). The mean chemical composition from bark vs. wood of P. curatellifolia was ash (3.2% vs. 1.6%), total extractives (12.2% vs. 10.0%), total lignin (42.4% vs. 28.4%), and suberin 5.4%. Families identified by GC-MS from DCM extracts were predominated by fatty acids in wood and triterpenoid contents in bark. Bark and wood had higher antioxidant activity in FRAP and DPPH methods. The bark had a monomeric lignin composition richer in guaiacyl-units (25.9% vs. 22.5%) and lower syringyl-units (5.7% vs. 8.5%). Potassium was the most abundant mineral, while the least was cadmium found in wood and bark. Regarding thermal properties, bark presented higher moisture content (9.0% vs. 8.0%), ash (3.33% vs. 1.61%), total volatiles (27.5% vs. 20.7%), lower fixed carbon (69.1% vs. 77.7%) and higher heating value (20.9 MJ/kg vs. 19.1 MJ/kg). According to these characteristics, both biomasses are interesting for developing more value-added products (e.g., charcoal, bio-chemicals with phytochemistry and pharmacology activities) besides burning under the context of biorefineries.