Using time-of-flight mass spectrometer (TOFMS), photochemistry of carbon tetrachloride clusters ((CCl₄)_n) has been investigated upon interaction with nanosecond and picosecond Nd:YAG laser pulses (266, 355, 532 and 1064 nm) spanning over intensity range of ~1.2 x 10⁹ to 7.9 x 10¹² W/cm². At all the laser wavelengths upon interaction of (CCl₄)_n clusters with laser pulse, multiphoton excitation leads to excessive fragmentation of cluster constituents, which are subsequently ionized by multiphoton absorption process. Depending on laser wavelength and pulse duration, at 266 and 355 nm these clusters exhibit dominant ion signal corresponding to singly charged fragment ions i.e. Cl⁺, CCl⁺, CCl₂⁺ and CCl₃⁺ in the mass spectra. In addition, for studies carried out at 266 nm using picosecond laser pulses minor ion signal corresponding to C₂Cl⁺ and C₂Cl₂⁺ were also observed. Generation of these ions has been ascribed to intra-cluster radical chemistry resulting in generation of neutral precursors, which subsequently are multiphoton ionized. At 532 and 1064 nm, dominant ion signal corresponding to multiply charged atomic ions of carbon (up to C⁴⁺/C⁵⁺) and chlorine (up to C¹¹⁺) have been observed. Though multiphoton absorption is the primary process driving the photochemistry of (CCl₄)_n clusters, observation of multiply charged atomic ions at 532 and 1064 nm has been ascribed to dominant role played by quasi-free electrons which are confined within the ionized cluster, in efficient coupling of laser energy at longer laser wavelengths via inverse Bremsstrahlung process.