Self-Q-switching (SQS) of lasers enable the generation of Q-switched pulses from simple laser cavities without using any additional saturable absorbers or active modulators. Earlier studies have reported SQS in ruby, Nd:YAG, and Cr:LiSAF lasers. However, these systems were mostly flashlamp pumped and required cooling of the crystal and/or misalignment of the laser cavity for the observation of SQS. In this presentation, for the first time to our knowledge, we report SQS operation of a Cr:LiCAF laser. SQS was achieved in an astigmatically compensated x-cavity containing only a Cr:LiCAF crystal that was end-pumped with a 140-mW continuous-wave (cw) diode at 660 nm. During regular cw operation, the laser produced a diffraction-limited beam with 50 mW of output power and had a spectral width of 0.5 nm near 795 nm. SQS operation of the Cr:LiCAF laser could be initiated by fine adjustment of the separation between the curved mirrors of the cavity and was observed at several mirror separations within the stability range of the resonator. During SQS operation, the laser generated saw-tooth-shaped pulses with 20-30 microsecond duration in the 780-800 nm wavelength range, at repetition rates between 10 and 30 kHz. SQS operation was further accompanied with a decrease in the output power to the 30-45 mW range. In this regime, the output beam became multimode and spectral broadening up to 12.5 nm (FWHM) was observed.