The Multicolor Simultaneous Camera for studying Atmospheres of Transiting exoplanets (MuSCAT) is an optical three-band (g_2-, r_2-, and z_{s,2}-band) imager that was recently developed for the 188cm telescope at Okayama Astrophysical Observatory with the aim of validating and characterizing transiting planets. In a pilot observation with MuSCAT we observed a primary transit of HAT-P-14b, a high-surface gravity (g_p=38 ms^{-2}) hot Jupiter around a bright (V=10) F-type star. From a 2.9 hr observation, we achieved the five-minute binned photometric precisions of 0.028%, 0.022%, and 0.024% in the g_2, r_2, and z_{s,2} bands, respectively, which provided the highest-quality photometric data for this planet. Combining these results with those of previous observations, we search for variations of transit timing and duration over five years as well as variations of planet-star radius ratio (R_p/R_s) with wavelengths, but can find no considerable variation in any parameters. On the other hand, using the transit-subtracted light curves we simulate achievable measurement error of R_p/R_s with MuSCAT for various planetary sizes, assuming three types of host stars: HAT-P-14, the nearby K dwarf HAT-P-11, and the nearby M dwarf GJ1214. Comparing our results with the expected atmospheric scale heights, we find that MuSCAT is capable of probing the atmospheres of planets as small as a sub-Jupiter (R_p ~6 R_Earth) around HAT-P-14 in all bands, a Neptune (~4R_Earth) around HAT-P-11 in all bands, and a super-Earth (~2.5R_Earth) around GJ1214 in r_2 and z_{s,2} bands. These results promise that MuSCAT will produce fruitful scientific outcomes in the K2 and TESS era.