The outgassing of volatile organic compounds during photoresist exposure at short wavelengths (<200 nm) has in recent years become a cause for concern as a source for contamination of lithographic optics and has triggered a significant investment of resources to understand and address the problem. In this paper, we report on Lincoln Laboratory’s contribution to this industry-wide effort with results from two types of outgassing measurements aimed at providing a better understanding of the risk posed by this phenomenon. The first method is a quantitative measurement based on a gas chromatograph-mass spectrometer and measures the outgassing by collecting the vapor sample over several minutes in order to enhance sensitivity. This first method cannot determine the outgassing time dependence over the duration of the exposure (~seconds). Our second method, based on laser desorption mass spectrometry, has been performed under UHV conditions to determine the time-dependence of photoresist outgassing and has shown that, for both 193- and 157-nm exposures, a majority of the total outgassed vapor is desorbed during the exposure time. The time dependence of the remaining amount that outgasses after exposure can be fit to a double exponential with characteristic time constants of ~0.5 and ~3 seconds, indicating that even in the limiting case of very short exposures (<<1 second), most material (>50%) would outgas within seconds. The implications of these findings are twofold. First, analytical methods used to measure outgassing that rely on long (>10 minute) sample collection and preconcentration steps must now assume that the measured product is liberated over a few-second time frame when converting the data to outgassing rates. This means that the peak transient outgassing rates for the few seconds during and immediately after exposure derived using this corrected method could be hundreds of times higher than previously reported, with values approaching as much as 1014 molecules/cm2-sec leading to transient concentrations well into the parts per million range. Second, given these higher rates, a review of lens purging designs should be done to ensure protection against these outgassing fluxes. In this paper we also discuss potentially new and unique issues caused by outgassing as they pertain to immersion and 157-nm lithographies that are currently under development.