Lithium ion conducting biodegradable gel polymer electrolytes based on a poly (ε-caprolactone):lithium tetrafluoroborate (PCL:LiBF4) system doped with various concentrations of 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) ionic liquid were prepared by solution cast technique. The gel polymer electrolyte was eco-friendly, flexible, transparent and free-standing. The conductivity and transference number measurements were carried out to investigate ionic conduction and charge transport in the gel polymer electrolytes. The frequency-dependent conductivity results revealed that the room-temperature electrical conductivity increased with increasing EMIMBF4 concentration. At room temperature, the gel polymer electrolyte with a composition of 85PCL:15LiBF4 + 40EMIMBF4 exhibited a high conductivity value of approximately 2.83 × 10−4 S cm−1, which was favored by the rich amorphous phase as confirmed with X-ray diffraction analysis. The lithium ion transport number and electrochemical stability of the 40 % EMIMBF4 gel polymer electrolyte were 0.43 and 3.7 V, respectively. These values are acceptable and quite enough for practical device applications. Consequently, the 40 wt% EMIMBF4 incorporated gel polymer electrolyte could be used to fabricate lithium ion batteries with a suitable selection of other components of the battery system.