Objectives To determine the degree of conversion (DC) over 48 h post-curing of resin mixtures containing trimethylbenzoyl-diphenylphosphine oxide (TPO) initiator cured by a polywave or a monowave LED light-curing unit (LCU). Methods In resin mixtures based on equal weight percent (wt%) of BisGMA and TEGDMA the following initiators were added: 0.2 wt% camphorquinone (CQ) + 0.8 wt% ethyl-4-dimethylaminobenzoate (EDMAB) (Group 1); 1 wt% TPO (Group 2) and 0.1 wt% CQ + 0.4 wt% EDMAB + 0.5 wt% TPO (Group 3). Half of the samples in each group ( n = 5) were cured using a polywave (bluephase ® G2, Ivoclar Vivadent) or a monowave LED LCU (bluephase ®, Ivoclar Vivadent). The DC was measured using micro-Raman spectroscopy within 5 min and then 1, 3, 6, 24 and 48 h post-irradiation. The data were analysed using general linear model and two-way ANOVA for the factors ‘time’, ‘material’, ‘surface’ and ‘LCU’ at α = 0.05. Results The initial DC values obtained upon light curing remained similar over a 48 h period. bluephase ® G2 produced the highest DC in Group 2 followed by Group 3, and Group 1. bluephase ® resulted in the highest DC in Group 1, followed by Group 2 and Group 3 ( p < 0.05). Conclusions Unfilled resin materials containing both TPO– and CQ–amine initiators are effectively cured using bluephase ® G2. Resin mixture with the same wt% of initiators is better cured when TPO is the only initiator, compared to CQ–amine only or combined TPO and CQ–amine system. After initial light cure, no additional conversion of uncured monomers was detected in an unfilled resin material over 48 h at 37 °C.