An experiment was conducted to investigate the effectiveness of calcium hydroxide (Ca(OH) 2) and urea treatment of straw. Chopped barley straw was treated with mixtures of Ca(OH) 2 (0, 30 and 60 g kg −1 straw dry matter, DM) and urea (0, 30 and 60 g kg −1 straw DM) dissolved in 0.81 water kg −1 straw DM and ‘ensiled’ in a polythene bag (1.0 kg per bag) at 15°C or 25°C for 60 days. Control treatment at each temperature involved untreated straw and treatment with 30 or 60 g NaOH kg −1 straw DM dissolved in 0.81 water kg −1 straw DM. Ensiled straws were examined for mould, chemically analysed and assessed for organic matter digestibility (OMD) in vitro. Mould occurred in Ca(OH) 2-alone and water-alone ensiled straw, but other ensiled straws were apparently mould free. In the presence of Ca(OH) 2 with urea treatment, the nitrogen content of ensiled straw increased more than urea-alone treatment. Analysis of variance of OMD in vitro results showed that Ca(OH) 2, urea and temperature interact significantly ( P < 0.01). Interactions were found to be non-significant for other parameters (nitrogen, acid detergent fibre and hemicellulose). However, straw ensiled at 15°C with 30 g urea +60 g Ca(OH) 2 kg −1 straw DM, 60 g urea +60 g Ca(OH) 2 kg −1 straw DM or 30 g NaOH kg −1 straw DM had similar OMD in vitro (67%). Untreated straw OMD was 48.5%. It can be concluded that mixtures of Ca(OH) 2 and urea would be the alternative chemicals to NaOH or ammonia for improvement of the nutritive value of straw.