The study presents an experimental investigation on the behavior of condensate film and liquid–vapor meniscus in the unit cell of a pulsating heat pipe (PHP) at different operating boundary conditions, and their respective roles in determining PHP’s performance. The orientation and the temperatures of evaporator and condenser sections are taken as the variable operating boundary conditions whereas the amplitude of oscillations influences the performance of the PHP. The entire thermo-hydrodynamic phenomenon is captured using high-speed imaging. By tracking the interface of liquid film and vapor, different regimes for film flow in the condenser section are observed and characterized. Also, the oscillation amplitude has been quantified at different operating boundary conditions. Despite a quite small tube diameter, gravity plays a key role in determining the liquid and vapor phase distributions in the tube. The variation of oscillation amplitude is intimately linked with the nuances of film flow regimes and inter-regime transitions. The optimum inclination angle, and evaporator and condenser temperatures are found to exist for the PHP unit cell which maximize the oscillation amplitude. The dependence of optimum inclination angle on condenser temperature has also been understood along with. Further, the associated film flow regime in condenser which facilitates these optima has also been recognized. All variable operating boundary conditions are observed to have a peculiarly mixed influence on the flow regimes and thus oscillation amplitude. The study would help to achieve a better elementary understanding of the role of condensate film flow in determining PHP’s performance and develop a flow regime map particularly for PHPs.