We present multi-instrument optical observations of the High Energy Transient Explorer (HETE-2)/Interplanetary Network (IPN) error box of GRB 010921. This event was the first gamma ray burst (GRB) localized by HETE-2 which has resulted in the detection of an optical afterglow. In this paper we report the earliest known observations of the GRB010921 field, taken with the 0.11-m Livermore Optical Transient Imaging System (LOTIS) telescope, and the earliest known detection of the GRB010921 optical afterglow, using the 0.5-m Sloan Digital Sky Survey Photometric Telescope (SDSS PT). Observations with the LOTIS telescope began during a routine sky patrol 52 minutes after the burst. Observations were made with the SDSS PT, the 0.6-m Super-LOTIS telescope, and the 1.34-m Tautenburg Schmidt telescope at 21.3, 21.8, and 37.5 hours after the GRB, respectively. In addition, the host galaxy was observed with the USNOFS 1.0-m telescope 56 days after the burst. We find that at later times (t > 1 day after the burst), the optical afterglow exhibited a power-law decline with a slope of \(\alpha = 1.75 \pm 0.28\). However, our earliest observations show that this power-law decline can not have extended to early times (t < 0.035 day).