Display omitted •Porous carbon nanospheres gel is adopted as carrier for SMIP preparation.•3D monolithic imprinted adsorbent material is obtained.•The boron–carbon grid provides excellent stability and durability.•The 3D monolithic structure ensures outstanding operability. By adopting porous carbon nanospheres gel (PCNS-gel) carrier, the corresponding 3D monolithic surface molecularly imprinted polymer adsorbent (SMIP@PCNS-gel) possesses unique advantages of excellent stability and efficient renewability besides its outstanding selectivity towards target phenol molecules. Carrier PCNS-gel is fabricated through the hydrothermal reaction of glucose, borax, and polyvinyl alcohol mixture. Based on the PCNS-gel, the functional adsorbent SMIP@PCNS-gel is obtained via surface molecular imprinting technology, with phenol as template molecule and methacrylic acid as functional monomer. Owing to the surface imprinted layer, SMIP@PCNS-gel performances a good adsorption capacity of 64.02 mg g−1 towards phenol. In addition, SMIP@PCNS-gel has good selectivity towards phenol in the quaternary mixture solution of phenol, hydroquinone, p-nitrophenol, and p-tert-butylphenol with relative selectivity factors of 3.04, 16.50, and 3.93, respectively. More importantly, thanks to the 3D monolithic PCNS-gel carrier, the SMIP@PCNS-gel adsorbent exhibits exceptional separation and recovery efficiency as well as outstanding stability and durability. The adsorption capacity only decreases by 10% after 10 repeated adsorption–desorption cycles. The adsorption capacity of SMIP@PCNS-gel towards phenol in alkaline wastewater with complex composition is 58.4 mg g−1. The prepared novel 3D monolithic SMIP@PCNS-gel adsorbent shows a promising application prospect for the deep and selective adsorption removal of phenol from wastewater.