We present a study of the photochemistry of abiotic habitable planets with anoxic CO2–N2 atmospheres. Such worlds are representative of early Earth, Mars, and Venus and analogous exoplanets. Photodissociation of H2O controls the atmospheric photochemistry of these worlds through production of reactive OH, which dominates the removal of atmospheric trace gases. The near-UV (NUV; >200 nm) absorption cross sections of H2O play an outsized role in OH production; these cross sections were heretofore unmeasured at habitable temperatures (<373 K). We present the first measurements of NUV H2O absorption at 292 K and show it to absorb orders of magnitude more than previously assumed. To explore the implications of these new cross sections, we employ a photochemical model; we first intercompare it with two others and resolve past literature disagreement. The enhanced OH production due to these higher cross sections leads to efficient recombination of CO and O2, suppressing both by orders of magnitude relative to past predictions and eliminating the low-outgassing "false-positive" scenario for O2 as a biosignature around solar-type stars. Enhanced [OH] increases rainout of reductants to the surface, relevant to prebiotic chemistry, and may also suppress CH4 and H2; the latter depends on whether burial of reductants is inhibited on the underlying planet, as is argued for abiotic worlds. While we focus on CO2-rich worlds, our results are relevant to anoxic planets in general. Overall, our work advances the state of the art of photochemical models by providing crucial new H2O cross sections and resolving past disagreement in the literature and suggests that detection of spectrally active trace gases like CO in rocky exoplanet atmospheres may be more challenging than previously considered.