We report the effect of radio frequency (RF) acetylene plasma on the dynamics and composition of titanium (Ti) plasma plume in a plasma-enhanced pulsed laser deposition (PEPLD) system. The titanium target, mounted inside a capacitively coupled RF discharge, was ablated by using a nanosecond Nd:YAG pulsed laser at 1064 nm with a power density of 2.65 GW/cm2. The experiments were performed at different operating pressures of acetylene. Fast imaging and optical emission spectroscopy were employed to study the physics behind the pulsed laser deposition in both (PLD) and PEPLD systems. A nonlinear dependence of the plasma plume evolution was observed over a range of pressure. Different expansion regimes correspond to the pressure of the experiments. The plume expansion velocity ranges between 6 × 103 m/s and 30 × 103 m/s. Emission spectra reveal the presence of C II and Ti II lines depending on the experimental conditions. The presence of background RF plasma leads to substantial enhancement of the emission intensity of the C II spectral lines. In addition, with increasing RF power and background pressure, the intensities of the C II spectral lines increase; whereas the intensities of the Ti II spectral lines decrease with the increase in RF power. Plasma temperature was estimated from the Ti II lines using the Boltzmann plot method, whereas the electron density was estimated from the Stark-broadened Ti II line at 454.9 nm. The calculated densities and temperatures lie between 1017–1018 cm−3 and 0.8–2.0 eV, respectively. These results show the effects of the different backgrounds (either neutral or RF plasma) on the propagation of the laser-produced plasma (LPP), which we propose to be useful in the thin film deposition process using PLD.