β-Tricalcium phosphate (TCP) is an osteoinductive and resorbable material that offers superior biochemical activity for bone regeneration therapies. TCP nanofiber scaffolds are particularly promising owing to their high porosity and chemical composition that resemble the mineral phase of natural extracellular matrix. TCP nanofiber scaffolds were fabricated by electrospinning. The nanofiber morphology promoted unidirectional grain growth during the sintering stage due to lack of surrounding grains in the other two principal directions. The average fiber diameter after sintering was 100–125 nm, which is the smallest grain size ever reported for TCP.