Rotationally resolved S-1<--S-0 fluorescence excitation spectra of 2-chloronaphthalene (2ClN) are measured using a newly constructed ultraviolet (UV) laser/molecular beam spectrometer. More than 1000 well-resolved rotational lines are recorded at a resolution of similar to3 MHz for the two overlapping band origins of the Cl-35 and Cl-37 isotopomers (Delta nu (origin)similar to3 GHz) over a 3.5 cm(-1) spectral region at a rotational temperature of 10 K. Both spectra are hybrid bands, having 18% a-/82% b-type character in accordance with L-1(a)<--(1)A(1) excitations observed for other 2-substituted naphthalenes. Additionally, Cl nuclear quadrupole splittings are observed as broadened asymmetric line shapes with linewidths from 5 to 20 MHz. Least-squares fits of these line shapes coupled with high-precision Fourier-transform microwave measurements of the ground state have provided accurate S-1 quadrupole coupling constants. Specified relative to the principal quadrupole tensor orientation of S-0, the S-0 and S-1 values of eQq(zz) are -71.198(5) MHz and -67.8(30) MHz, and the asymmetry parameters, eta=(eQq(yy)-eQq(xx))/eQq(zz), are 0.076 38(5) and 0.13(5), respectively. The experimental line shapes are fit to Voigt functions, yielding 4.9(3) MHz homogeneous (lifetime) and 3.0(2) MHz inhomogeneous (Doppler) contributions. All of the observed structure are well reproduced by more than 20 000 transitions predicted for the nuclear-quadrupole-split rotational spectra of the two hybrid-band origins. Furthermore, the homogeneous linewidths show no dependence on either the upper state energy or angular momentum quantum numbers. The absence of additional level structure at the resolution of 1 MHz or more, from heavy-atom-enhanced intersystem crossing mechanisms, is discussed within the framework of radiationless transition theory. The quadrupole tensor components are used in simple theoretical models to investigate the orbital character of the S-1 state and its radiationless decay mechanisms.