This study presents the first successful demonstration of growing elemental bismuth (Bi) thin films via thermal atomic layer deposition (ALD) using Bi(NMe₂)₃ as the precursor and Sb(SiMe₃)₃ as the co-reactant. The films were deposited at a relatively low temperature of 100 °C, with a growth per cycle (GPC) of 0.31–0.34 Å/cycle. Island formation marked the initial growth stages, with surface coverage reaching around 80 % after 1000 cycles and full coverage between 2000 and 2500 cycles. Morphological analysis revealed that the Bi grains expanded and became more defined as the number of ALD cycles increased. This coalescence is further supported by X-ray diffraction (XRD) patterns, which show a preferential shift in growth orientation from the (012) plane to the (003) plane as the film thickness increases. X-ray photoemission spectroscopy (XPS) confirmed the presence of metallic Bi with minimal surface oxidation. Temperature-dependent sheet resistance measurements highlight the semimetallic nature of Bi, with a room temperature resistivity of ≈200 μΩcm for the 2500 cycles Bi. Temperature-dependent sheet resistance was also associated with a transition in carrier-type dominance from holes at higher temperatures to electrones at lower temperatures.