The cooling of ionic species in the gas phase greatly simplifies the UV spectrum, which is of special importance when studying the electronic and geometric structures of large systems, such as biorelated molecules and hostguest complexes. Many efforts have been devoted to achieving ion cooling with a cold, quadrupole Paul ion trap (QIT), but one problem was the insufficient cooling of ions (up to similar to 30 K) in the QIT. In this study, we construct a mass spectrometer for the ultraviolet photodissociation (UVPD) spectroscopy of gas-phase cold ions. The instrument consists of an electrospray ion source, a QIT cooled with a He cryostat, and a time-of-flight mass spectrometer. With great care given to the cooling condition, we can achieve similar to 10 K for the vibrational temperature of ions in the QIT, which is estimated from UVPD spectra of the benzo-18-crown-6 (B18C6) complex with a potassium ion, K+.B18C6. Using this setup, we measure a UVPD spectrum of cold calix[4]arene (C4A) complex with potassium ion, K+.C4A. The spectrum shows a very weak band and a strong one at 36018 and 36156 cm(-1), respectively, accompanied by many sharp vibronic bands in the 36000-36600 cm(-1) region. In the geometry optimization of the K+.C4A complex, we obtain three stable isomers: one endo and two exo forms. On the basis of the total energy and UV spectral patterns predicted by density functional theory calculations, we attribute the structure of the K+.C4A complex to the endo isomer (C-2 symmetry), in which the K+ ion is located inside the cup of C4A. The vibronic bands of K+.C4A at 36 018 and 36 156 cm(-1) are assigned to the S-1(A)-S-0(A) and S-2(B)-S-0(A) transitions of the endo isomer, respectively.