Collagen modification of scaffolds has been reported to promote matrix mineralization as an effective way to increase osseointegration of implants. The aim of this study was to investigate in vitro proliferation and differentiation of human alveolar osteoblasts (AOs) on medical-grade polycaprolactone–tricalcium phosphate (mPCL-TCP 80:20) scaffolds after collagen modification (mPCL-TCP-c) for 28 days. Collagen modification significantly increased the scaffold’s protein adsorption ability, and improved the initial seeding efficiency and cell attachment at day 1, compared with non-collagen-modified scaffolds. However, the total DNA content of both groups reached similar levels with no significant difference at 28 days’ culture. AOs were observed to spread along the collagen fibres and form extensive collagenous fibres with mineral nodules embedded, while multilayered cell sheets were formed in mPCL-TCP scaffolds. During culture, alkaline phosphatase (ALP) activity increased three- to five-fold in both groups, and collagen modification did not significantly affect either the metabolic rate or ALP activity kinetics of AOs. During osteogenic differentiation, similar gene expression of collagen type-I, osterix, osteopontin, and osteocalcin were detected in both groups. The mPCL-TCP group showed better organized mineralized tissue, but the mPCL-TCP-c showed more scattered and unorganized tissue. These results indicate that collagen modification improved the scaffold’s protein adsorption ability and encouraged initial cell attachment and distribution, but promoted fibrous-like tissue formation rather than mineralized tissue.