We present medium resolution (lambda/Delta lambda = 2500) optical spectroscopy of SN 1999by in NGC 2841 made around its light maximum. The depth ratio of the two Si II features at 5800 AA and 6150 AA being R(SiII) approx. 0.63 at maximum indicates that this SN belongs to the peculiar, sub-luminous SNe Ia. Radial velocities inferred from the minimum of the 6150 AA trough reveal a steeper decline of the velocity curve than expected for ``normal SNe Ia, consistent with the behavior of published VRI light curves. A revised absolute magnitude of SN 1999by and distance to its host galaxy NGC 2841 is estimated based on the Multi-Color Light Curve Shape (MLCS) method, resulting in M_V(max)=-18.06+/- 0.1 mag and d = 17.1+/-1.2 Mpc, respectively. An approximative linear dependence of the luminosity parameter Delta on R(SiII) is presented.