Nine doublet Λ-S states of calcium monochloride (CaCl) are calculated using the internally contracted multireference configuration interaction method with the Davidson correction. Both the core subvalence and spin-orbit coupling effects are taken into account. Laser cooling of CaCl and production of ultracold chlorine atoms are investigated and assessed. Our computed spectroscopic constants and radiative lifetimes match the available experimental data very well. The determined Franck-Condon factors and vibrational branching ratios of the A(2)Π1/2(ν('))←X(2)Σ1/2 (+)(ν) transition are highly diagonally distributed and the evaluated radiative lifetime for the A(2)Π1/2(ν' = 0) state is 28.2 ns, which is short enough for rapid laser cooling. Subsequently, detection of cold molecules via resonance enhanced multiphoton ionization to determine the final quantum state populations is discussed and the ionization energy calculated. A multi-pulse excitation scheme is proposed for producing ultracold chlorine atoms from zero-energy photodissociation of the cooled CaCl. Our results demonstrate the possibility of producing ultracold CaCl molecules and Cl atoms.