The current work presents the d33,eff evaluation for Ba0·9Ca0·1Ti0·9Zr0·1O3 (BCZT) thin film (TF) prepared by RF magnetron sputtering over Pt (111) substrate by switching spectroscopy piezo-response force microscopy (SS-PFM). Our results reveal an d33.eff approximately of 70 p.m. V−1. This value was compared with the bulk ceramic counterpart (d33.eff = 72 p.m. V−1), and it is comparable with other similar lead-free TF compositions. To understand the d33.eff value for the TF, the influence of mixed-valence Ti (Ti3+ and Ti4+) states and oxygen chemical ions is elucidated by x-ray photoelectron spectroscopy (XPS). The component analysis for Ti 2p and O 1s XPS regions confirmed a less presence of oxygen O− ions in the TF. X-ray diffraction corroborates the tetragonal perovskite structure with P4mm space group, which is desired to obtain ferroelectric properties. The good piezo-response for the TF is very promising as a storage device for the electronic industry.