The effect of temperature and pressure on the nucleation of the vapor phase and the velocity of the vapor front in the initial stage of activated boiling-up of n-pentane on the surface of a quartz fiber was studied. Using a developed approach combining the “pump-probe” and laser Doppler velocimetry methods, this velocity was tracked in the course of sequential change in the degree of superheating with respect to the liquid–vapor equilibrium line. The studied interval according to the degree of superheating was 40–100 °C (at atmospheric pressure). In order to spatiotemporally localize the process, the activation of boiling-up at the end of the light guide was applied using a short nanosecond laser pulse. A spatial locality of measurements was achieved in units of micrometers, along with a time localization at the level of nanoseconds. An increase in temperature at a given pressure was found to lead to an increase in the speed of the transition process with a coefficient of about 0.2 m/s per degree, while an increase in pressure at a given temperature leads to a decrease in the transition process speed with a coefficient of 25.8 m/s per megapascal. The advancement of the vapor front velocity measurements to sub-microsecond intervals from the first signs of boiling-up did not confirm the existence of a Rayleigh expansion stage with a constant velocity.