Nonlinear refractive properties of chloroaluminum phthalocyanine (CAP) in ethanol solution are studied using the Z-scan technique with picosecond (ps) and nanosecond (ns) laser pulses at a wavelength of 532 nm. A transition from self-focusing to self-defocusing in CAP solution excited by 10 ns pulses is observed during the decrease of its concentration. This transition is due to co-existing excited-state refraction and transient thermal lensing effects. The experimental results are described very well using the rate-equation model and the theory of transient thermal refraction in liquids. The refractive cross sections of the excited-state are also obtained.