Biochar may serve as a tool to sustainably mitigate climate change via carbon sequestration and by improving soil fertility. Biochar has shown to retain nitrate in its pores, which increases with an organic coating of the inner surfaces and residence time in soil (“aging”). Here we investigated the plant accessibility of the captured nitrate in field-aged biochar, as a pre-requisite for developing carbon-based N fertilization techniques with environmental benefits. Based on previous results, we hypothesized that part of the biochar-captured nitrate would remain unavailable for plants. A two-factorial greenhouse experiment was designed, where the N was applied either as Ca(NO3)2 or as N captured in field-aged biochar at five increasing N doses to quinoa and perennial ryegrass in pots. Interestingly, the biochar-captured N was as plant available as the mineral nitrate, except for the highest dosage. Refuting our hypothesis, no significant amounts of N were extractable at the end of the study from the biochar–soil mixtures with repeated-extraction protocols. Thus, N captured by biochar may improve the N use efficiency in agriculture. Further research should evaluate the role of biochar particle size, root morphology, mycorrhization, and soil moisture (variations) for nitrate retrieval from biochar particles by plants because the captured biochar N was less available in the field as under present controlled conditions.