The main objective of this work was the preparation and optimization of boron-doped diamond-like carbon (DLC) films having a good crystalline structure, and electronic and optical properties, at an extremely low deposition pressure and relatively low growth temperature, by varying the flow rates of precursor gases (CH4, B2H6, and Ar) in the plasma controlled at 800 W of RF power. Planar inductively coupled plasma-enhanced chemical vapour deposition technique was used to enable deposition at ∼5.33 Pa and 450 °C, at a constant negative substrate bias of -40 V. The flow rate of the dopant gas (B2H6) was changed to obtain a set of samples, while the precursor gas (CH4) flow rate was kept fixed. The doped sample, prepared with B2H6/CH4 ratio (r) = 1%, was found to possess a minimum ID/IG (intensity ratio of D peak with that of G peak) of ∼0.819 and a maximum IDia/IG ratio (relative intensity of the Diamond peak to that of the G peak) of ∼1.149. A high sp3 content of ∼50% was revealed from the X-ray photoelectron spectroscopy analysis and the transmission electron microscopy images also indicated the presence of prominent <111>, <220>, and <311> crystallographic planes. The B-doped DLC film possessed enhanced electrical conductivity (σRT) of ∼3.02 × 10−5 S cm−1 relative to intrinsic DLC films, a corresponding minimum of activation energy (ΔEH) (as calculated in the above room temperature regime) of ∼170 meV, an optical band gap (Eg) of ∼3.35 eV, and the root mean square roughness of ∼48.12 nm.