Time-resolved photoelectron spectroscopy is a well established method of femtosecond spectroscopy able to reveal ultrafast electronic relaxation by a significant change of the photoionization channel as a function of the delay. Otherwise femtosecond photoexcitation often involves multiphoton ionization. This paper illustrates a singular two-photon ionization process insensitive to vibrational energy and involving ubiquitous doubly excited states encountered at high energy just below the ionization potential (IP). The population of these multielectronic excited states decays via an Auger-like process to a set of Rydberg states. This fast and efficient internal conversion takes place within the probe duration such that the Rydberg states can be photoionized by the absorption of a subsequent probe photon. The photoelectron spectrum is then characterized by a Rydberg fingerprint. This process will be illusrated in azulene, methyl iodine and nitrogen dioxide.