The impact of additions (1–5% by weight) of a nutrient-poor, wood-derived biochar on pepper (Capsicum annuum L.) and tomato (Lycopersicum esculentum Mill.) plant development and productivity in a coconut fiber:tuff growing mix under optimal fertigation conditions was examined. Pepper plant development in the biochar-treated pots was significantly enhanced as compared with the unamended controls. This was reflected by a system-wide increase in most measured plant parameters: leaf area, canopy dry weight, number of nodes, and yields of buds, flowers and fruit. In addition to the observed increases in plant growth and productivity, the rhizosphere of biochar-amended pepper plants had significantly greater abundances of culturable microbes belonging to prominent soil-associated groups. Phylogenetic characterization of unique bacterial isolates based on 16S rRNA gene analysis demonstrated that of the 20 unique identified isolates from roots and bulk soil from the char-amended growing mix, 16 were affiliated with previously described plant growth promoting and/or biocontrol agents. In tomato, biochar treatments positively enhanced plant height and leaf size, but had no effect on flower and fruit yield. The positive impacts of biochar on plant response were not due to direct or indirect effects on plant nutrition, as there were no differences between control and treatments in leaf nutrient content. Nor did biochar affect the field capacity of the soilless mixture. A number of organic compounds belonging to various chemical classes, including n-alkanoic acids, hydroxy and acetoxy acids, benzoic acids, diols, triols, and phenols were identified in organic solvent extracts of the biochar. We conjecture two related alternatives to explain the improved plant performance under biochar treatment: (i) the biochar stimulated shifts in microbial populations towards beneficial plant growth promoting rhizobacteria or fungi, due to either chemical or physical attributes of the biochar; or (ii) low doses of biochar chemicals, many of which are phytotoxic or biocidal at high concentrations, stimulated plant growth at low doses (hormesis).