Dijet angular distributions from the first LHC pp collisions at center-of-mass energy sqrt(s) = 7 TeV have been measured with the ATLAS detector. The dataset used for this analysis represents an integrated luminosity of 3.1 pb-1. Dijet distributions and centrality ratios have been measured up to dijet masses of 2.8 TeV, and found to be in good agreement with Standard Model predictions. Analysis of the distributions excludes quark contact interactions with a compositeness scale below 3.4 TeV, at 95% confidence level, significantly exceeding previous limits.