Nowadays, most of the works are based on electric vehicle usage for sustainable transportation using traditional energy storage device, such as battery. Usage of batteries in electric vehicles is having several disadvantages, for example, life span, temperature, and charge estimation. In this paper, a novel control scheme for battery and supercapacitor‐ (SC‐) based hybrid energy storage system (HESS) using hybrid proportional and integral‐ (PI‐) sliding mode control (SMC) for electric vehicle (EV) applications is introduced and implemented. This HESS with hybrid controller proves the usage of batteries in EVs to its fullest potential. The conventional control strategy for HESS follows two‐loop voltage and current PI controllers with low‐pass filter (LPF) and involves tuning of multiple control parameters with variations of source and load disturbances. Performance of the system is affected by tuning PI controller constants. A slow response time with linear PI controllers is long which is not advisable for starting and sudden jerk conditions of EVs. Moreover, the PI controller performance is affected by the system parameter variations during load changes. And these parameters are dynamic in nature due to nonideal conditions. In this paper, a hybrid PI‐sliding mode controller (SMC) scheme is designed to control the bidirectional DC‐DC converters to overcome the drawbacks of aforementioned issues. The combined PI‐SMC controller reduces the tuning effort and reduces the effect of shift in operating point in controller performance. Linear modeling is done using small signal analysis for each subsystems. Permanent magnet synchronous machine (PMSM) is used as electric vehicle. The entire system and its controllers are simulated using MATLAB‐Simulink, and detailed comparison is carried between conventional PI and proposed hybrid PI‐SMC scheme to regulate the DC link voltage. The results are tabulated and show that the hybrid PI‐SMC scheme outperforms in transient and steady‐state conditions than the traditional PI controller. A scaled hardware prototype of 48 W set‐up is developed using dSPACE‐1104, and the experimental results have been carried out to verify the proposed system’s feasibility.