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• Boron-doped graphene is synthetized from pulse laser co-ablation of boron and carbon. • Thermal annealing converts the boron-doped carbon precursor in boron-doped graphene. • The synthesis route allows a precise control of the boron concentration in graphene. • The boron-doped graphene film contains mainly 2–3 layers. • Boron doping modifies the defect concentration in the graphene film. Incorporating dopants, such as boron, in graphene, is crucial for many applications in electrochemistry, sensors, photovoltaics, and catalysis. Many routes have been investigated for the preparation of B-doped graphene (BG) films, including chemical processes. A different way to obtain boron-doped layers to better control the concentration of boron in the doped graphene film, is pulsed laser co-ablation of C and B solid sources followed by rapid thermal heating of the B-doped carbon film deposited on a metal catalyst. Amorphous a-C:B films, containing 2 at. % boron, are synthetized by pulse laser deposition onto a nickel film catalyst. Rapid thermal annealing at 1100 °C leads to the formation of boron-doped graphene films, characterized by Raman, XPS, FEG-SEM, HRTEM and AFM. The results confirm the production of 1–4 layer boron doped graphene films, with a similar 2 at. % boron concentration to that of the a-C:B used as the graphene solid precursor. Boron doping does not modify the nano-architecture of graphene, but increases the concentration of defects in the films. Our results pave a new way for boron doped graphene synthesis using laser processing in a controlled and reproducible way, in particular to achieve designed electrical and chemical properties in various electronic and electrochemical applications. [ABSTRACT FROM AUTHOR]