Yes, you can read and write directly to an EBS volume from an EC2 instance. They are block devices, and follow all the expected semantics.
In practical terms, you cannot read from or write to an EBS volume other than through the EC2 instance to which it is attached. Again, they are block devices... there's no mechanism of access other than by attaching them to an EC2 instance.
Although... snapshotting an EBS volume does not require that it be attached to an instance, which means it is possible to take a snapshot of a volume, and then use the EBS Direct API to read raw data from the snapshot, so technically it's possible to read from an EBS volume with no EC2 instance attached, albeit indirectly and pretty convoluted. With this, you can read but not write.