Based on long-term high-resolution spectroscopic observations obtained during five observing runs from 2001 to 2004, we study optical flare events and chromospheric activity variability of the very active RS CVn star UX Ari. By means of the spectral subtraction technique, several optical chromospheric activity indicators (including the He I D-3, Na I D-1, D-2 doublet, H alpha and Ca II IRT lines) covered in our echelle spectra were analyzed. Four large optical flare events were detected on UX Ari during our observations, which show prominent He I D-3 line emission together with great enhancement in emission of the H alpha and Ca II IRT lines and strong filled-in or emission reversal features in the Na I D-1, D-2 doublet lines. The newly detected flares are much more energetic than previous discoveries, especially for the flare identified during the 2002 December observing run. Optical flare events on UX Ari are more likely to be observed around two quadratures of the system, except for our optical flares detected during the 2004 November observing run. Moreover, we have found rotational modulation of chromospheric activity in the H alpha and Ca II IRT lines, which suggests the presence of chromospherically active longitudes over the surface of UX Ari. The change in chromospherically active longitudes among our observing runs, as well as the variation in chromospheric activity level from 2001 to 2004, indicates a long-term evolution of active regions.