We used photon pulses from an x-ray free-electron laser to study ultrafast x-ray-induced transitions of graphite from solid to liquid and plasma states. This was accomplished by isochoric heating of graphite samples and simultaneous probing via Bragg and diffuse scattering at high time resolution. We observe that disintegration of the crystal lattice and ion heating of up to 5 eV occur within tens of femtoseconds. The threshold fluence for Bragg-peak degradation is smaller and the ion-heating rate is faster than current x-ray-matter interaction models predict. [2,3], and in high-energy-density science [4]. Triggered by intense photon pulses in the laboratory, such phase transitions are complex. The kinetics of optical photoninduced transitions has been studied extensively [1,5,6]. Optical photons are absorbed through collective electronic processes [7]. In contrast, x-ray-induced dynamics are expected to differ substantially because x rays generate high-energy photoelectrons that equilibrate through collisional ionization and develop into a hot electron gas. Additionally, x rays penetrate materials to depths of more than 1 m, whereas optical penetration depths are rather short ($ 10 nm). The emergence of x-ray free-electron lasers (XFELs) now enables the study of ultrafast x-rayinduced transitions at extremely high time resolution and over a large, isochorically heated volume.We used pulses from an XFEL to excite graphite isochorically to extreme conditions with electron temperatures up to about 10 eV [8]. This induced ultrafast electronic processes and, ultimately, an order-disorder transformation. We characterized the x-ray-induced ultrafast ionization, lattice destruction, and temperaturerelaxation dynamics with a temporal resolution of tens of femtoseconds by measuring the dynamic structure factor, Sðk; !Þ, simultaneously both on and off the Bragg resonance. At low x-ray intensities, the crystal structure stays intact, the Bragg peak is very strong, and diffuse scattering is weak. With increasing intensities, the Bragg peak degrades due to atomic ionization and motion, and the forward diffuse elastic-scattering signal increases correspondingly. The combined measurements of the pulse-width dependence and fluence dependence of these signals allowed us to extract the ion temperature as a function of time.We performed the experiments at the Linac Coherent Light Source (LCLS) [9], using an x-ray energy of 2 keV, pulse energies of up to 2.8 mJ, and pulse durations of 40, 60, and 80 fs. We determined the multiple-shot averaged x-ray pulse duration from statistical analysis of single-shot spectra within an error of 30% [10]. The pulse energy was measured for each shot using an upstream nitrogenfluorescence detector [11]. The transmission of the beam line was about ð15 AE 3Þ% [12]. The focal spot area was determined from microscopic analysis of low-fluence beam imprints in yttrium aluminum garnet [13]. We focused the x-ray pulses to a beam area of 36-10 m 2 onto a highly oriented pyrolytic-graphite (HOPG) crystal, a...