We present femtosecond transient transmission measurements of thin films of the V-II/III-Cr-III Prussian blue analogue (V-Cr PBA) in the spectral range 330-675 nm after exciting the ligand-to-metal charge-transfer transition (LMCT) at 400 nm. A global analysis including three decay-times of tau(1) = 230 fs, tau(2) = 1.38 ps and tau(3) >> 2 ns could satisfactory describe the data. We observed an excited state absorption (ESA) at 345 nm, which was attributed to a charge-transfer transition from the E-2 state on the Cr ions after fast intersystem crossing from the quartet manifold. An additional weak and short-lived ESA at 455 nm was also observed and was tentatively attributed to the initially populated (LMCT)-L-4 state. Crown Copyright (C) 2017 Published by Elsevier B.V. All rights reserved.