The bridge molecule thiourea (TU) enforced polyaniline (PANI) growing on activated carbon fiber (ACF) is applied to synthesize polyaniline-thiourea-activated carbon fiber (PANI-TU-ACF) through surface activation, hydrothermal treatment and electrochemical deposition processes for wearable braidable-supercapacitor. Experimental measurement and theoretical calculation demonstrate that PANI-TU-ACF involves amide bonding interface between ACF and TU and hydrogen bonding interface between TU and PANI, thus confirming the formation of bridging structure. The absorption spectrum red-shift of N-H vibration peak keeps in agreement with the declined bonding energy of N-H bond achieved by partial atom potential simulation calculation, which proves the formation of hydrogen bonding in PANI-TU-ACF. PANI-TU-ACF exhibits larger N(E) value and lower HOMO-LUMO energy gap than PANI-ACF, indicating its higher electrical conductivity. PANI-TU-PANI shows more lowered interface energy than PANI-ACF, suggesting its higher stability. PANI-TU-ACF electrode delivers excellent capacitance of 563.8 F g-1 at 1 A g-1 and cycling stability of 89.1% for 2000 cycles. Wearable braidable-supercapacitor based on PANI-TU-ACF electrode delivers energy density of 62.9 Wh kg-1 at power density of 800 W kg-1, maintains high capacitance retention of 90.13% after 2000 charging/discharging cycles. The interfacial bonding strengthened PANI-TU-ACF with excellent performance displays potential in wearable supercapacitors.