In the presented research facile, sensitive and accurate electrochemical method i.e. differential pulse voltammetry is described for evaluating the release kinetics of caffeine (CAF) from 3D bioactive polymeric scaffolds with application in bone tissue engineering. For the preparation of composite filaments (polylactide - caffeine) in a mass ratio 9:1 and 3D scaffolds Filastruder v1.0 extruder and RepRapPro Tricolor Mendel 3D printer were applied. All produced 3D structures fully reproduce virtual models. The amounts of caffeine released from filaments and scaffolds were analyzed for 96 h in deionized water, 0.1 mol . L-1 phosphate buffer saline (PBS, pH 7.4) and 0.1 mol . L-1 HCl. UV-Vis spectrophotometry was used as a reference method according to the recommendation of European pharmacopoeia (9th ed., 2016). For both methods selectivity, sensitivity, precision and accuracy were specified. Differential pulse voltammetry technique has proved to be competitive and to have high sensitivity, greater range of linearity, short analysis time, easy operation and low cost meeting the requirements of green analytical chemistry contrary to UV-Vis spectrophotometry. (C) 2018 The Electrochemical Society.