The initial growth during the atomic-layer deposition (ALD) of Al2O3 using trimethylaluminum (TMA) and water was studied on two starting surfaces: SiO2 and -H-terminated Si(111) [H/Si(111)]. In situ spectroscopy ellipsometry (SE) showed virtually immediate growth of Al2O3 on both surfaces, although for H/Si(111) a reduced growthper-cycle was observed in the initial 20 cycles. The underlying surface chemistry during the initial cycles of ALD was monitored with in situ broadband sum-frequency generation (BB-SFG) spectroscopy. For the SiO2 surface, the -CH3 surface groups were followed revealing that only the first TMA half-cycle deviates from the steady-growth regime. The reaction cross section of the initial TMA half-cycle (sigma(TMA) = 2.0 +/- 0.2 X 10(-18) cm(2)) was a factor of 3 lower than the cross section of the TMA half-cycle during the steady-growth regime of ALD (sigma(TMA), = 6.5 +/- 0.6 X 10(-18) cm(2)). All H2O half-cycles, including the first, showed steady-growth behavior with a corresponding reaction cross section (sigma(H2O) = 4.0 +/- 0.4 X 10(-20) cm(2)). Therefore, only the first ALD cycle was affected by initial growth effects on the SiO2 starting surface, in line with the SE data. For the H/Si(111) surface, the Si-H groups were monitored with BB-SFG spectroscopy, revealing a reaction cross section of sigma(TMA) = 3.1 +/- 0.3 X 10(-18) cm(2) for the first TMA half-cycle on H/Si(111); a factor two lower than that during the steady regime of Al2O3. These results demonstrate that the chemistry during the initial growth regime of Al2O3 ALD on SiO2 and H/Si(111) shows subtle but measurable differences compared to the steady-growth regime.